U.S. patent application number 13/500247 was filed with the patent office on 2012-08-09 for cellulose resin and method for producing the same.
This patent application is currently assigned to NEC CORPORATION. Invention is credited to Masatoshi Iji, Hiroyuki Kai, Sungil Moon, Shukichi Tanaka.
Application Number | 20120202926 13/500247 |
Document ID | / |
Family ID | 43856735 |
Filed Date | 2012-08-09 |
United States Patent
Application |
20120202926 |
Kind Code |
A1 |
Iji; Masatoshi ; et
al. |
August 9, 2012 |
CELLULOSE RESIN AND METHOD FOR PRODUCING THE SAME
Abstract
A cellulose resin produced by binding cardanol or a derivative
thereof to cellulose or a derivative thereof with the use of a
cellulose hydroxy group of the cellulose or a derivative thereof
and the phenolic hydroxy group of the cardanol or a derivative
thereof.
Inventors: |
Iji; Masatoshi; (Minato-ku,
JP) ; Moon; Sungil; (Minato-ku, JP) ; Tanaka;
Shukichi; (Minato-ku, JP) ; Kai; Hiroyuki;
(Minato-ku, JP) |
Assignee: |
NEC CORPORATION
Minato-ku, Tokyo
JP
|
Family ID: |
43856735 |
Appl. No.: |
13/500247 |
Filed: |
October 4, 2010 |
PCT Filed: |
October 4, 2010 |
PCT NO: |
PCT/JP2010/067333 |
371 Date: |
April 4, 2012 |
Current U.S.
Class: |
524/41 ;
536/82 |
Current CPC
Class: |
C08B 3/16 20130101; C08B
3/10 20130101; C08B 3/22 20130101; C08B 13/00 20130101 |
Class at
Publication: |
524/41 ;
536/82 |
International
Class: |
C08L 1/12 20060101
C08L001/12; C08B 3/22 20060101 C08B003/22 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 5, 2009 |
JP |
2009-231670 |
Apr 30, 2010 |
JP |
2010-105509 |
Jul 8, 2010 |
JP |
2010-156238 |
Claims
1. A cellulose resin produced by binding cardanol or a derivative
thereof to cellulose or a derivative thereof with the use of a
cellulose hydroxy group of the cellulose or a derivative thereof
and a phenolic hydroxy group of the cardanol or a derivative
thereof.
2. The cellulose resin according to claim 1, wherein: a cellulose
carbon atom to which the cellulose hydroxy group is bound and a
cardanol carbon atom to which the phenolic hydroxy group is bound
are linked via an organic linking group, and the organic linking
group comprises a first bond binding to the cellulose carbon atom,
the first bonding being selected from an ester bond, an ether bond
and a urethane bond, and a second bond binding to the cardanol
carbon atom, the second bonding being selected from an ester bond,
an ether bond and a urethane bond.
3. The cellulose resin according to claim 2, wherein the first bond
is an ester bond and the second bond is an ester bond or an ether
bond.
4. The cellulose resin according to claim 2, wherein the organic
linking group comprises a divalent hydrocarbon group having 1 to 20
carbon atoms.
5. The cellulose resin according to claim 4, wherein: the cellulose
carbon atom and the hydrocarbon group are bound via an ester bond
as the first bond, and the cardanol carbon atom and the hydrocarbon
group are bound via an ester bond or an ether bond as the second
bond.
6. The cellulose resin according to claim 1, wherein number DSCD of
the cardanol molecules or a derivative thereof added to the
cellulose or a derivative thereof per glucose unit is 0.1 or
more.
7. The cellulose resin according to claim 1, wherein, to a
cellulose hydroxy group of the cellulose or a derivative thereof, a
reactive hydrocarbon compound comprising a functional group capable
of reacting with the cellulose hydroxy group is added.
8. The cellulose resin according to claim 7, wherein the reactive
hydrocarbon compound is a hydrocarbon compound comprising a
carboxyl group, a carboxylic halide group or a carboxylic acid
anhydride group.
9. The cellulose resin according to claim 7, wherein the reactive
hydrocarbon compound is at least one monocarboxylic acid, an acid
halide thereof or acid anhydride thereof, the monocarboxylic acid
being selected from an aliphatic carboxylic acid, an aromatic
carboxylic acid and an alicyclic carboxylic acid.
10. The cellulose resin according to claim 7, wherein the reactive
hydrocarbon compound is at least one monocarboxylic acid selected
from an aromatic carboxylic acid and an alicyclic carboxylic acid,
an acid halide or acid anhydride thereof.
11. The cellulose resin according to claim 7, wherein number DSXX
of the reactive hydrocarbon compound molecules added to the
cellulose or a derivative thereof per glucose unit is 0.1 or
more.
12. The cellulose resin according to claim 1, wherein at least one
acyl group selected from an acetyl group, a propionyl group and a
butyryl group is added to a cellulose hydroxy group of the
cellulose or a derivative thereof.
13. The cellulose resin according to claim 1, wherein: to a
cellulose hydroxy group of the cellulose or a derivative thereof,
at least one first acyl group selected from an acetyl group, a
propionyl group and a butyryl group, and a second acyl group
derived from at least one monocarboxylic acid selected from an
aromatic carboxylic acid and an alicyclic carboxylic acid are
added; and number DSXX of the second acyl groups added to the
cellulose or a derivative thereof per glucose unit is 0.1 or
more.
14. The cellulose resin according to claim 1, wherein, number DSOH
of remaining cellulose hydroxy groups per glucose unit is 0.9 or
less.
15. The cellulose resin according to claim 1, wherein, a sum of the
cellulose component and the cardanol component is 50% by mass or
more, based on the total amount of the resin.
16. The cellulose resin according to claim 1, wherein an
unsaturated bond of the cardanol or a derivative thereof is
hydrogenated.
17. A resin composition comprising the cellulose resin as recited
in claim 1 as a base resin.
18. A resin composition comprising the cellulose resin as recited
in claim 1 and a thermoplastic polyurethane elastomer.
19. A resin composition comprising the cellulose resin as recited
in claim 1 and a modified silicone compound.
20. A molding material comprising the resin composition as recited
in claim 17.
21. A method for producing a cellulose resin, comprising: reacting
a multifunctional compound capable of reacting with a hydroxy group
of cellulose and a phenolic hydroxy group of cardanol, with
cardanol to form a cardanol derivative; and reacting the cardanol
derivative with cellulose or a derivative thereof to bind the
cardanol derivative to the cellulose or a derivative thereof.
22. The method for producing a cellulose resin according to claim
21, wherein the multifunctional compound comprises a hydrocarbon
group having 1 to 20 carbon atoms.
23. The method for producing a cellulose resin according to claim
21, wherein the multifunctional compound comprises a functional
group selected from the group consisting of a carboxyl group, a
carboxylic halide group, a carboxylic acid anhydride group, an
epoxy group, an isocyanate group and a halogen group.
24. The method for producing a cellulose resin according to claim
21, wherein the multifunctional compound comprises a functional
group selected from the group consisting of a carboxyl group, a
carboxylic acid anhydride group and a halogen group.
25. The method for producing a cellulose resin according to claim
21, wherein the multifunctional compound is a compound comprising a
carboxylic acid anhydride group, or a compound comprising a
carboxyl group and a halogen group.
26. The method for producing a cellulose resin according to claim
21, wherein: the multifunctional compound comprises a carboxyl
group or a carboxylic acid anhydride group, and the process further
comprises converting a carboxyl group of the cardanol derivative
into a carboxylic halide group, after forming the cardanol
derivative.
27. The method for producing a cellulose resin according to claim
21, further comprising hydrogenating an unsaturated bond of the
cardanol or a derivative thereof.
28. The method for producing a cellulose resin according to claim
21, wherein a reactive hydrocarbon compound comprising a functional
group capable of reacting with the cellulose hydroxy group is
reacted with the cellulose or a derivative thereof, simultaneously
or separately with the cardanol derivative, to bind the reactive
hydrocarbon compound to the cellulose or a derivative thereof
29. The method for producing a cellulose resin according to claim
28, wherein the reactive hydrocarbon compound is a hydrocarbon
compound comprising a carboxyl group, a carboxylic halide group or
a carboxylic acid anhydride group.
30. The method for producing a cellulose resin according to claim
28, wherein the reactive hydrocarbon compound is at least one
monocarboxylic acid, an acid halide thereof or acid anhydride
thereof, the monocarboxylic acid being selected from an aliphatic
carboxylic acid, an aromatic carboxylic acid and an alicyclic
carboxylic acid.
Description
TECHNICAL FIELD
[0001] The present invention relates to a cellulose resin and a
method for producing the same.
BACKGROUND ART
[0002] Bioplastic using a plant as a raw material can contribute to
a countermeasure against petroleum depletion and global warming,
and has been started being used not only in common products such as
packaging, containers and fibers but also in durable products such
as electronics and automobiles.
[0003] However, general bioplastics, such as polylactic acid,
polyhydroxyalkanoate and modified starch, all use starch materials,
more precisely, edible parts, as raw materials. Accordingly, for
fear of future food shortage, it has been desired to develop a
novel bioplastic using a non-edible part as a raw material.
[0004] As bioplastic using a non-edible part as a raw material,
various types of bioplastics using cellulose, which is a main
component of non-edible parts of wood and plant, have been already
developed and commercialized.
[0005] Cellulose is a high molecular weight compound formed by
polymerization of .beta.-glucose. Since cellulose has high
crystallinity, it is hard, fragile and absent of thermoplasticity.
In addition, since cellulose contains many hydroxy groups, water
absorbability is high and water resistance is low. Then, various
investigations have been made to improve the properties of
cellulose.
[0006] For example, Patent Literature 1 (JP11-255801A) discloses a
biodegradable graft polymer having thermoplasticity obtained by
ring-opening graft polymerization of cellulose acetate having a
hydroxy group with .epsilon.-caprolactone.
[0007] Meanwhile, a material using a non-edible component other
than cellulose has been developed. For example, cardanol derived
from cashew nutshell, since it has stable amount of production and
excellent functionality ascribed to its characteristic molecular
structure, has found various applications.
[0008] As an example of using cardanol, Patent Literature 2
(JP10-8035A) discloses a friction material for brake, which is
formed of a fiber base material made of an aramid pulp and a
cellulose fiber, and a filler made of calcium carbonate and cashew
dust, with the use of a binder made of a phenol resin. Patent
Literature 3 (JP2001-32869A) discloses a friction material formed
of a base material made of an aramid fiber and a cellulose fiber,
and a filler made of graphite and cashew dust, with the use of an
organic-inorganic composite binder. It is described that the
friction material is applied to clutch facing of a power
transmission system of automobiles etc.
[0009] In Non Patent Literature 1 (George John et al., Polymer
Bulletin, 22, p. 89-94 (1989)), it is described that water
resistance of paper can be improved by soaking a paper sheet in
cardanol to perform a grafting reaction through which cardanol
binds to cellulose constituting the paper sheet. It is described
that, in the grafting reaction, a terminal double bond of cardanol
binds to a hydroxy group of cellulose in the presence of boron
trifluoride diethyl ether (BF.sub.3--OEt.sub.2).
CITATION LIST
Patent Literature
[0010] Patent Literature 1: JP11-255801A [0011] Patent Literature
2: JP10-8035A [0012] Patent Literature 3: JP2001-32869A
Non Patent Literature
[0012] [0013] Non Patent Literature 1: George John et al., Polymer
Bulletin, 22, p. 89-94 (1989)
SUMMARY OF INVENTION
Technical Problem
[0014] Cellulose bioplastic, whose properties are influenced by
inherent properties of cellulose, is insufficient in strength, heat
resistance, water resistance and thermoplasticity. These properties
need to be improved particularly when cellulose bioplastic is
applied to durable products such as packaging for electronic
devices.
[0015] Cellulose bioplastic has another problem. When a plasticizer
is added in order to improve thermoplasticity, heat resistance and
strength (in particular, rigidity) decrease, and also decrease in
uniformity and bleed out of a plasticizer (a plasticizer bleeds out
in the surface of a compact) occur. Furthermore, when a plasticizer
formed of a petroleum feedstock is added in a large amount, the
utilization ratio of plants (vegetism) decreases.
[0016] An object of the present invention is to provide a cellulose
resin having improved thermoplasticity, mechanical characteristics
and water resistance and having a high vegetism and a high
utilization ratio of a non-edible part, and to provide a method for
producing the cellulose resin.
Solution to Problem
[0017] According to an exemplary aspect, there is provided a
cellulose resin produced by binding cardanol or a derivative
thereof to cellulose or a derivative thereof with the use of a
cellulose hydroxy group of the cellulose or a derivative thereof
and the phenolic hydroxy group of the cardanol or a derivative
thereof
[0018] According to another exemplary aspect, there is provided a
molding material including the above cellulose resin as a base
resin.
[0019] According to another exemplary aspect, there is provided a
resin composition including the above cellulose resin and a
thermoplastic polyurethane elastomer or a modified silicone
compound.
[0020] According to another exemplary aspect, there is provided a
method for producing a cellulose resin, including:
[0021] reacting a multifunctional compound capable of reacting with
a hydroxy group of cellulose and the phenolic hydroxy group of
cardanol, with cardanol to form a cardanol derivative, and
[0022] reacting the cardanol derivative with cellulose or a
derivative thereof to bind the cardanol derivative to the cellulose
or a derivative thereof.
Advantageous Effects of Invention
[0023] According to the present invention, it is possible to
provide a cellulose resin having improved thermoplasticity,
mechanical characteristics and water resistance and having a high
vegetism and a high utilization ratio of a non-edible part, and to
provide a method for producing the cellulose resin.
DESCRIPTION OF EMBODIMENTS
[0024] According to an exemplary embodiment, a cellulose resin is
obtained by binding cardanol (or a derivative thereof) to cellulose
(or a derivative thereof) in the form of graft (hereinafter
referred to as "grafting").
[0025] Owing to such grafting, mechanical characteristics
(particularly toughness) and water resistance can be improved.
Furthermore, since good thermoplasticity is provided by the
grafting, the amount of plasticizer to be added can be reduced or a
plasticizer may not be added. As a result, heat resistance and
strength (particularly rigidity) can be suppressed from reducing
compared to the cellulose resin containing a plasticizer, and
homogeneity of the resultant resin can be improved. In addition, a
problem of bleed out can be overcome. Furthermore, since the
addition amount of plasticizer made of a petroleum feedstock can be
lowered or reduced to zero, vegetism can be enhanced. In addition,
since cellulose and cardanol are both derived from non-edible parts
of plants, the utilization ratio of non-edible parts can be
increased.
[0026] Cellulose is a straight-chain polymer of .beta.-glucose,
represented by the following formula (1) and each glucose unit has
three hydroxy groups. Using these hydroxy groups, cardanol (or a
derivative thereof) can be grafted.
[Formula 1]
##STR00001##
[0028] Cellulose is a main component of plants and can be obtained
by a separation treatment for removing other components such as
lignin from the plants. Other than the cellulose thus obtained,
cellulose obtained by purification of cotton or pulp rich in
cellulose content can be used, or the cotton or pulp can be
directly used.
[0029] The polymerization degree of cellulose (or a derivative
thereof) preferably falls within the range of 50 to 5000 and more
preferably 100 to 3000 in terms of glucose polymerization degree.
If the polymerization degree is extremely low, the strength and
heat resistance of the produced resin may not be sufficient in some
cases. Conversely, if the polymerization degree is extremely high,
the melt viscosity of the produced resin is extremely high,
interfering with molding in some cases.
[0030] Cellulose (or a derivative thereof) may be mixed with chitin
and chitosan having an analogous structure. When cellulose is mixed
with them, the amount thereof is preferably 30% by mass or less
relative to the total amount of mixture, preferably 20% by mass or
less and further preferably 10% by mass or less.
[0031] A cellulose derivative herein refers to cellulose having
hydroxy groups partly acylated, etherified or grafted. Specific
examples thereof include organic acid esters such as cellulose
acetate, cellulose butyrate and cellulose propionate; inorganic
acid esters such as cellulose nitrate, cellulose sulfate and
cellulose phosphate; mixed esters such as cellulose acetate
propionate, cellulose acetate butyrate, cellulose acetate phthalate
and cellulose acetate nitrate; and etherified cellulose such as
methylcellulose, hydroxyethylcellulose and hydroxypropylcellulose.
Furthermore, celluloses grafted with styrene, (meth)acrylic acid,
(meth)acrylate, .epsilon.-caprolactone, lactide, glycolide, etc.
These acylated cellulose, etherified cellulose and grafted
cellulose may be used singly or in combination of two or more
types.
[0032] As the cellulose (or a derivative thereof) of the exemplary
embodiment, for example, at least one acylated cellulose selected
from a cellulose acetate, cellulose propionate and cellulose
butyrate, which have hydroxy groups partially acylated, can be
preferably used.
[0033] The term "cellulose derivative" used herein includes both a
cellulose compound and a compound having a cellulose skeleton
obtained by biologically or chemically introducing a functional
group into raw-material cellulose.
[0034] Cardanol is a component contained in the shell of cashew
nut, and is an organic compound represented by the following
formula (2), which has a phenol moiety and a straight-chain
hydrocarbon moiety. There are 4 types of cardanols different in the
number of unsaturated bonds in the straight-chain hydrocarbon
moiety R. Usually, cardanol is a mixture of these 4 components. To
be more specific, cardanol is a mixture of 3-pentadecylphenol,
3-pentadecylphenol monoene, 3-pentadecylphenol diene and
3-pentadecylphenol triene, described in the following formula (2).
A cardanol component obtained by extracting and purifying from a
cashew nutshell liquid can be used.
##STR00002##
[0035] R: --(CH.sub.2).sub.14CH.sub.3 [0036]
--(CH.sub.2).sub.7CH.dbd.CH(CH.sub.2).sub.5CH.sub.3 [0037]
--(CH.sub.2).sub.7CH.dbd.CHCH.sub.2CH.dbd.CH(CH.sub.2).sub.2CH.sub.3
[0038]
(CH.sub.2).sub.7CH.dbd.CHCH.sub.2CH.dbd.CHCH.sub.2CH.dbd.CH.sub.2
[0039] The straight-chain hydrocarbon moiety of cardanol
contributes to improving flexibility and hydrophobicity of a resin,
whereas the phenol moiety has a highly reactive phenolic hydroxy
group for use in grafting. When such cardanol (or a derivative
thereof) is grafted to cellulose (or a derivative thereof), a
cellulose structure to which cardanol (or a derivative thereof) is
added like bristles is formed. As a result, cardanol bristles thus
grafted interact with each other to improve mechanical
characteristics (particularly toughness), as well as to impart
thermoplasticity. In addition, owing to hydrophobicity of cardanol,
water resistance can be improved.
[0040] Grafting can be performed through a binding reaction by
dehydration between the phenolic hydroxy group of cardanol (or a
derivative thereof) and a hydroxy group of cellulose (or a
derivative thereof). At this time, a dehydration catalyst such as
sulfuric acid, toluene sulfonic acid and hydrogen chloride can be
added. As a result, a cellulose carbon atom to which a hydroxy
group of cellulose (or a derivative thereof) is bound and a
cardanol carbon atom to which the phenolic hydroxy group of
cardanol (or a derivative thereof) is bound are linked via an
oxygen atom.
[0041] Also, grafting can be performed by use of a multifunctional
compound capable of reacting with a hydroxy group of cellulose and
the phenolic hydroxy group of cardanol. As a result, a cellulose
carbon atom to which a hydroxy group of cellulose (or a derivative
thereof) is bound and a cardanol carbon atom to which the phenolic
hydroxy group of cardanol (or a derivative thereof) is bound are
linked via an organic linking group. According to such grafting,
efficiency of a grafting reaction can be improved and a side
reaction can be suppressed.
[0042] The organic linking group may have a first bond binding to
the cellulose carbon atom, the bond being selected from an ester
bond, an ether bond and a urethane bond, and a second bond binding
to the cardanol carbon atom, the bond being selected from an ester
bond, an ether bond and a urethane bond.
[0043] For example, this multifunctional compound and cardanol are
bound by use of the phenolic hydroxy group of cardanol and one of
the functional groups of the multifunctional compound, and the
resultant cardanol derivative and cellulose (or a derivative
thereof) can be bound by use of a hydroxy group of cellulose (or a
derivative thereof) and the functional group (the functional group
derived from the multifunctional compound) of the cardanol
derivative.
[0044] According to the aforementioned grafting, the hydroxy group
of cellulose (or a derivative thereof) and the hydroxy group of
cardanol (or a derivative thereof) are eliminated to form a graft
bond; at the same time, the hydrophobic structure of cardanol can
be introduced into cellulose (or a derivative thereof) to improve
water resistance.
[0045] To graft cardanol (or a derivative thereof) to cellulose (or
a derivative thereof), the phenolic hydroxy group of cardanol and a
hydroxy group of cellulose are preferably used as mentioned above
in view of efficiency of a grafting reaction, resultant molecular
structure and water resistance. Since such grafting is made by use
of a highly-reactive phenolic hydroxy group, more efficient
grafting can be realized compared to grafting using an unsaturated
bond (double bond) of the straight-chain hydrocarbon moiety of
cardanol. Furthermore, according to the grafting of the exemplary
embodiment, since the phenol moiety of cardanol reacts with
cellulose and fixed to it, interaction between mutual
straight-chain hydrocarbon moieties of the grafted cardanol
molecules enhances, and thus a desired effect of improving
mechanical characteristics can be obtained. Furthermore, in the
exemplary embodiment, grafting is performed by eliminating the
phenolic hydroxy group of cardanol, water resistance can be
improved (suppressing water absorbability) compared to grafting
that does not use a phenolic hydroxy group. Also from this point of
view, the grafting of the exemplary embodiment is advantageous.
[0046] The aforementioned multifunctional compounds and organic
linking groups preferably include a hydrocarbon group. The number
of carbon atoms of the hydrocarbon group is preferably 1 or more
and more preferably 2 or more, and also preferably 20 or less, more
preferably 14 or less and further preferably 8 or less. If the
number of carbon atoms is excessively large, the molecule becomes
excessively large and thus reactivity reduces. As a result, it is
often difficult to increase a grafting rate. As such a hydrocarbon
group, a divalent group is preferable. Examples thereof include a
divalent straight-chain aliphatic hydrocarbon groups (particularly,
straight-chain alkylene group) such as a methylene group, an
ethylene group, a propylene group, a butylene group, a
pentamethylene group, a hexamethylene group, a heptamethylene
group, an octamethylene group, a decamethylene group, a
dodecamethylene group and a hexadecamethylene group; divalent
alicyclic hydrocarbon groups such as a cycloheptane ring group, a
cyclohexane ring group, a cyclooctane ring group, a bicyclopentane
ring group, a tricyclohexane ring group, a bicyclooctane ring
group, a bicyclononane ring group and a tricyclodecane ring group;
divalent aromatic hydrocarbon groups such as a benzene ring group,
a naphthalene ring group and a biphenylene group; and divalent
groups composed of combinations of these.
[0047] When the hydrocarbon group as mentioned above is an aromatic
hydrocarbon group or an alicyclic hydrocarbon group, because of its
stiffness, the rigidity of the resultant resin can be improved. In
contrast, when the hydrocarbon group is a straight-chain aliphatic
hydrocarbon group, because of its flexibility, the toughness of the
resultant resin can be improved.
[0048] As a functional group of a multifunctional compound as
mentioned above, a group selected from a carboxyl group, a
carboxylic acid anhydride group, a carboxylic halide group
(particularly, carboxylic chloride group), an acryl group, an epoxy
group, an isocyanate group and a halogen group is preferred. Of
them, a carboxyl group, a carboxylic acid anhydride group, a
halogen group (particularly, a chloride group) and an isocyanate
group are preferred. As the functional group to be reacted with the
phenolic hydroxy group of cardanol, particularly, a carboxylic acid
anhydride group, a halogen group (particularly, chloride group) and
an isocyanate group are preferred. As the functional group to be
reacted with a hydroxy group of cellulose, particularly, a
carboxylic halide group (particularly, a carboxylic chloride
group), an acid anhydride group, an acryl group and an isocyanate
group are preferred. The carboxylic halide group can be formed by
converting a carboxyl group before grafting into an acid halide
group. The acid anhydride group may be an oligomer composed of acid
anhydrides.
[0049] Specific examples of such a multifunctional compound include
dicarboxylic acid, carboxylic acid anhydride, dicarboxylic acid
halide, monochlorocarboxylic acid, acrylic acid and a derivative
thereof, and diisocyanates. Examples of the dicarboxylic acid
include malonic acid, succinic acid, glutaric acid, pimelic acid,
suberic acid, azelaic acid, sebacic acid, dodecane dicarboxylic
acid, pentadecane dicarboxylic acid and hexadecane dicarboxylic
acid. Examples of the carboxylic acid anhydride include anhydrides
of these dicarboxylic acids and maleic anhydride. The maleic
anhydride may be an oligomer composed of maleic anhydrides.
Examples of the dicarboxylic acid halide include acid halides of
these dicarboxylic acids. Examples of the monochlorocarboxylic acid
include monochloroacetic acid, 3-chloropropionic acid,
3-fluoropropionic acid, 4-chlorobutyric acid, 4-fluorobutyric acid,
5-chlorovaleric acid, 5-fluorovaleric acid, 6-chlorohexanoic acid,
6-fluorohexanoic acid, 8-chlorooctanoic acid, 8-fluorooctanoic
acid, 12-chlorododecanoic acid, 12-fluorododecanoic acid,
18-chlorostearic acid and 18-fluorostearic acid. Examples of the
acrylic acid and a derivative thereof include acrylic acid, acrylyl
chloride, methacrylic acid and methacrylyl chloride. Examples of
the diisocyanates include tolylene diisocyanate (TDI),
4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene
diisocyanate (NDI), tolidine diisocyanate, 1,6-hexamethylene
diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene
diisocyanate (XDI), hydrogenated XDI, triisocyanate,
tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane
triisocyanate, 1,8-diisocyanatemethyloctane, lysine ester
triisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane
triisocyanate and dicyclohexylmethane diisocyanate (HMDI:
hydrogenated MDI). Of these, tolylene diisocyanate (TDI),
4,4'-diphenylmethane diisocyanate (MDI) and 1,6-hexamethylene
diisocyanate (HDI) can be preferably used.
[0050] One of the functional groups of a multifunctional compound
as mentioned above and the phenolic hydroxy group of cardanol are
reacted to form a cardanol derivative, and then, the cardanol
derivative is bound to cellulose (or a derivative thereof) by use
of a hydroxy group of cellulose (or a derivative thereof) and the
functional group (derived from the multifunctional compound) of the
cardanol derivative.
[0051] For example, a carboxylic acid-based multifunctional
compound (dicarboxylic acid, carboxylic acid anhydride or
monochloro carboxylic acid) is reacted with cardanol, the phenolic
hydroxy group of the cardanol and a functional group of the
multifunctional compound (carboxyl group, carboxylic acid anhydride
group or halogen group (particularly, chloride group)) are reacted
to form a cardanol derivative, and the remaining functional group
(carboxyl group) is converted into a carboxylic halide group
(particularly, carboxylic chloride group). The cardanol derivative
is reacted with cellulose (or a derivative thereof) to react a
hydroxy group of the cellulose (or a derivative thereof) with the
carboxylic halide group of the cardanol derivative. In this way,
grafting can be performed. In this case, grafting can be extremely
efficiently performed.
[0052] As a result of grafting using a multifunctional compound,
the cellulose carbon atom to which a hydroxy group of cellulose (or
a derivative thereof) is bound and the hydrocarbon group of a
multifunctional compound are allowed to bind, for example, via an
ester bond, an ether bond or a urethane bond, preferably via an
ester bond; whereas the cardanol carbon atom to which the phenolic
hydroxy group of cardanol (or a derivative thereof) is bound and
the hydrocarbon group of the multifunctional compound are allowed
to bind, for example, via an ester bond, an ether bond or a
urethane bond, preferably via an ester bond or an ether bond.
[0053] An unsaturated bond(s) (double bond) of the straight-chain
hydrocarbon moiety of the cardanol are preferably hydrogenated and
converted into a saturation bond. The conversion rate
(hydrogenation rate) of the unsaturated bonds by hydrogenation is
preferably 90% by mole or more and more preferably 95% by mole or
more. After hydrogenation, the residual ratio (the number of
unsaturated bonds per cardanol molecule) of unsaturated bonds of
the cardanol is preferably 0.2 (bonds/molecule) or less and more
preferably 0.1 (bond/molecule) or less. Furthermore, the aromatic
ring of the phenol moiety of cardanol may be hydrogenated and
converted into a cyclohexane ring.
[0054] When cardanol (or a derivative thereof), in which a large
number of unsaturated bonds still remain in the straight-chain
hydrocarbon moiety, is grafted to cellulose (or a derivative
thereof), a side reaction likely to occur, with the result that
grafting cannot be efficiently performed and the solubility of a
grafted product in a solvent may often significantly reduce. When a
cardanol derivative in which an unsaturated bond(s) of the
straight-chain hydrocarbon moiety are sufficiently converted into
saturated bonds by hydrogenation, is grafted, grafting can be
efficiently performed while suppressing a side reaction and in
addition, solubility reduction of a grafted product in a solvent
can be suppressed.
[0055] The hydrogenation method is not particularly limited and a
method known in the art can be used. Examples of the catalyst
include a precious metal such as palladium, ruthenium and rhodium,
nickel, and a substance made by immobilizing a metal selected from
these on a carrier such as activated carbon, activated alumina and
diatom earth. As the reaction system, a batch system in which a
reaction is performed while suspending and stirring a powdery
catalyst and a continuous system using a reaction tower charged
with a molded catalyst can be employed.
[0056] The solvent for hydrogenation may not be used depending upon
the system of hydrogenation. However, when a solvent is used,
examples of the solvent include alcohols, ethers, esters and
saturated hydrocarbons generally. The reaction temperature for
hydrogenation is not particularly limited; however, it can be
usually set to 20 to 250.degree. C. and preferably 50 to
200.degree. C. If the reaction temperature is excessively low, a
hydrogenation rate becomes low. Conversely, if the reaction
temperature is excessively high, the amount of decomposition
product may increase. The hydrogen pressure during the
hydrogenation can be usually set to 10 to 80 kgf/cm.sup.2
(9.8.times.10.sup.5 to 78.4.times.10.sup.5 Pa) and preferably 20 to
50 kgf/cm.sup.2 (19.6.times.10.sup.5 to 49.0.times.10.sup.5
Pa).
[0057] Hydrogenation can be performed before the cardanol
derivative is formed, after the cardanol derivative is formed and
before the cardanol derivative is grafted, or after the cardanol
derivative is grafted; however, in view of the reaction efficiency
of hydrogenation and grafting reaction, hydrogenation is preferably
performed before the cardanol derivative is grafted and further
preferably before the cardanol derivative is formed.
[0058] The ratio (grafting rate) of cardanol (or a derivative
thereof) bound to cellulose (or a derivative thereof) relative to
the cellulose (or a derivative thereof) is represented by the
number (average value) of cardanol molecules (or a derivative
thereof) to be added per glucose unit of cellulose (or a derivative
thereof), in other words, the number (average value) of hydroxy
groups bound to cardanol molecules (or a derivative thereof) per
glucose unit of cellulose (or a derivative thereof) (the degree of
substitution of the hydroxy group, DS.sub.CD). DS.sub.CD) is
preferably 0.1 or more, and more preferably 0.2 or more. DS.sub.CD
may be set to 0.4 or more. When DS.sub.CD is excessively low, the
effect by grafting may not be sufficiently obtained.
[0059] The maximum value of DS.sub.CD is theoretically "3";
however, in view of facilitating production (grafting), DS.sub.CD
is preferably 2.5 or less, more preferably 2 or less and further
preferably 1.5 or less. Furthermore, DS.sub.CD may be 1 or less;
even in this case, sufficient improvement effect can be obtained.
If DS.sub.CD increases, tensile breaking strain (toughness) tends
to increase; whereas, the maximum strength (tensile strength,
bending strength) tends to decrease. Accordingly, DS.sub.CD is
preferably set appropriately in accordance with desired
properties.
[0060] Cardanol (or a derivative thereof) is grafted, and further a
specific reactive hydrocarbon compound may be grafted to cellulose
(or a derivative thereof). Owing to this, a cellulose resin can be
improved so as to have desired properties.
[0061] This reactive hydrocarbon compound is a compound having at
least one functional group capable of reacting with a hydroxy group
of cellulose (or a derivative thereof). Examples thereof include
hydrocarbon compounds having a carboxyl group, a carboxylic halide
group, a carboxylic acid anhydride group, an isocyanate group and
an acryl group. Specific examples thereof include at least one
compound selected from monocarboxylic acids such as an aliphatic
monocarboxylic acid, an aromatic monocarboxylic acid and an
alicyclic monocarboxylic acid, and acid halides or acid anhydrides
thereof; at least one compound selected from an aliphatic
monoisocyanate, an aromatic monoisocyanate and an alicyclic
monoisocyanate; an acrylic acid ester; and a methacrylic acid
ester. Examples of the aliphatic monocarboxylic acid include
straight and branched (having a side chain) fatty acids. Examples
of the aromatic monocarboxylic acid include an aromatic
monocarboxylic acid having a carboxyl group directly bound to an
aromatic ring, and an aromatic monocarboxylic acid having a
carboxyl group bound to the aromatic ring via an alkylene group
(for example, methylene group, ethylene group) (the acid having an
aliphatic carboxylic acid group bound to the aromatic ring).
Examples of the alicyclic monocarboxylic acid include an alicyclic
monocarboxylic acid having a carboxyl group directly bound to an
alicycle, and an alicyclic monocarboxylic acid having a carboxyl
group bound to an alicycle via an alkylene group (for example,
methylene group, ethylene group)(the acid having an aliphatic
carboxylic acid group bound to an alicycle). Examples of the
aliphatic monoisocyanate include an aliphatic monoisocyanate
obtained by reacting an aliphatic diisocyanate and a straight or
branched (having a side chain) aliphatic monoalcohol in a molar
ratio of 1:1. Examples of the aromatic monoisocyanate include an
aromatic monoisocyanate obtained by reacting an aromatic
diisocyanate and a straight or branched (having a side chain)
aliphatic monoalcohol in a molar ratio of 1:1. Examples of the
acrylic acid ester and methacrylic acid ester include esters of an
acrylic acid or methacrylic acid with a straight or branched
(having a side chain) aliphatic monoalcohol.
[0062] The reactive hydrocarbon compound preferably has carbon
atoms within the range of 1 to 32 and more preferably within the
range of 1 to 20. If the number of carbon atoms is excessively
large, the size of the molecule becomes excessively large and
reaction efficiency decreases due to steric hindrance. As a result,
it becomes difficult to increase a grafting rate.
[0063] The reactive hydrocarbon compound is effective in improving
properties in the case where it is particularly arranged so as to
bury gaps in a sterical structure of a grafted cardanol (or a
derivative thereof).
[0064] When the hydrocarbon group of the reactive hydrocarbon
compound is an aromatic hydrocarbon group and an alicyclic
hydrocarbon group, it efficiently works to particularly improve
rigidity and heat resistance. When the hydrocarbon group is an
aliphatic hydrocarbon group, it efficiently works to particularly
improve toughness.
[0065] Examples of the aliphatic monocarboxylic acid to be used as
the reactive hydrocarbon compound include saturated fatty acids
such as acetic acid, propionic acid, butyric acid, valeric acid,
caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric
acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid,
tridecylic acid, myristic acid, pentadecylic acid, palmitic acid,
heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid,
behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid,
montanic acid, melissic acid and lacceric acid; unsaturated fatty
acids such as butenoic acid, pentenoic acid, hexenoic acid,
octenoic acid, undecylenic acid, oleic acid, sorbic acid, linoleic
acid, linolenic acid and arachidonic acid; and derivatives of
these. These may further have a substituent.
[0066] Examples of the aromatic monocarboxylic acid used as the
reactive hydrocarbon compound include an aromatic carboxylic acid
having a carboxyl group introduced in a benzene ring such as
benzoic acid; an aromatic carboxylic acid having an alkyl group
introduced in a benzene ring such as toluic acid; an aromatic
carboxylic acid having an aliphatic carboxylic acid group
introduced in a benzene ring such as phenylacetic acid and phenyl
propionic acid; an aromatic carboxylic acid having two or more
benzene rings such as biphenylcarboxylic acid and biphenylacetic
acid; an aromatic carboxylic acid having a condensed-ring structure
such as naphthalene carboxylic acid and tetralin carboxylic acid;
and derivatives of these.
[0067] Examples of the alicyclic monocarboxylic acid to be used as
the reactive hydrocarbon compound include an alicyclic
monocarboxylic acid having a carboxyl group introduced to an
alicycle such as cyclopentane carboxylic acid, cyclohexane
carboxylic acid and cyclooctane carboxylic acid; alicyclic
monocarboxylic acids having an aliphatic carboxylic acid introduced
in an alicycle such as cyclohexyl acetic acid; and derivatives of
these.
[0068] If an organic silicon compound and an organic fluorine
compound are added to these reactive hydrocarbon compound
structures, properties such as water resistance can be more
effectively improved.
[0069] As the reactive functional groups of these reactive
hydrocarbon compounds, any reactive functional groups are used as
long as they can react with a hydroxy group of cellulose. Examples
thereof include a carboxyl group, a carboxylic acid halide group
(particularly, a carboxylic acid chloride group), and a carboxylic
acid anhydride, and further include an epoxy group, an isocyanate
group and a halogen group (particularly, a chloride group). Of
these, a carboxyl group and a carboxylic halide group are
preferable and a carboxylic acid chloride group is particularly
preferable. Examples of the carboxylic acid halide group
(particularly, a carboxylic acid chloride group) include an acid
halide group (particularly, an acid chloride group) in which a
carboxyl group of each of the carboxylic acids mentioned above is
acid-halogenated.
[0070] As the reactive hydrocarbon compound used in the exemplary
embodiment, particularly in view of rigidity (bending strength,
etc.) of a resin, at least one monocarboxylic acid selected from
aromatic carboxylic acids and alicyclic carboxylic acids, or an
acid halide or acid anhydride thereof are preferable. By adding
such a reactive hydrocarbon compound to a cellulose hydroxy group,
a structure formed by adding an acyl group derived from at least
one monocarboxylic acid selected from aromatic carboxylic acids and
alicyclic carboxylic acids to a cellulose hydroxy group (i.e., a
structure obtained by substituting a hydrogen atom of cellulose
hydroxyl group with an acyl group) can be obtained.
[0071] The number (average value) of reactive hydrocarbon compounds
(the number of acyl groups) to be added per glucose unit of
cellulose (or a derivative thereof), in other words, the number
(average value) of hydroxy groups bound to a reactive hydrocarbon
compound per glucose unit (the degree of substitution of the
hydroxy group, DS.sub.XX) is, in view of obtaining a desired
effect, preferably 0.1 or more and 0.6 or less and more preferably
0.1 or more and 0.5 or less. Furthermore, after cardanol (or a
derivative thereof) and a reactive hydrocarbon compound are
grafted, the number (average value) of remaining hydroxy groups per
glucose unit (hydroxy group remaining degree, DS.sub.OH) is, in
view of sufficiently ensuring water resistance, preferably 0.9 or
less and more preferably, 0.7 or less.
[0072] The reactive hydrocarbon compound can be grafted in the
grafting step of cardanol (or a derivative thereof). Owing to this,
grafting can be made uniformly. At this time, these may be added
simultaneously or separately. However, if cardanol (or a derivative
thereof) is grafted and thereafter a reactive hydrocarbon compound
is added and grafted, the efficiency of a grafting reaction can be
improved.
[0073] A grafting treatment can be performed by heating cellulose
(or a derivative thereof) and cardanol (or a derivative thereof),
if necessary, a reactive hydrocarbon compound in a solvent
dissolving them at an appropriate temperature. Cellulose is rarely
dissolved in a general solvent; however dissolved in e.g., a
dimethylsulfoxide-amine solvent, a
dimethylformamide-chloral-pyridine solvent, a
dimethylacetamide-lithium chloride solvent and an imidazolium ionic
liquid. When a grafting reaction is performed in a general solvent,
a cellulose derivative, the solubility of which has been changed by
previously binding a carboxylic acid or an alcohol to a part of
hydroxy groups of cellulose to reduce intermolecular force, can be
used. Acylated cellulose, in which the hydrogen atom of a hydroxy
group is substituted with an acyl group such as an acetyl group, a
propionyl group and a butyryl group, is preferable. In particular,
cellulose acetate, which is a cellulose acetylated by acetic acid
or acetyl chloride, is preferable. Acetic acid, propionic acid,
butyric acid and an acid halide and acid anhydride thereof are
included in the aforementioned reactive hydrocarbon compounds;
however, like this example, whole or part of predetermined reactive
hydrocarbon compounds can be added (grafted) to a hydroxy group of
cellulose before grafting with cardanol (or a derivative
thereof).
[0074] The remaining cellulose hydroxy group that is not used in
grafting cardanol (or a derivative thereof) is a hydroxy group
without being modified, a hydroxy group to be modified by
acetylation, or a hydroxy group to which a reactive hydrocarbon
compound is added (grafted). As the amount of hydroxy group
increases, maximum strength and heat resistance tend to increase;
whereas water absorbability tends to increase. As the conversion
rate (degree of substitution) of hydroxy groups increases, water
absorbability tends to decrease, plasticity and breaking strain
tend to increase; whereas, maximum strength and heat resistance
tend to decrease. In consideration of these tendencies and grafting
conditions, the conversion rate of hydroxy groups can be
appropriately set.
[0075] In view of ensuring sufficient water resistance, the number
(average value) of remaining hydroxy groups of a cellulose resin
grafted per glucose unit (hydroxy group remaining degree,
DS.sub.OH) is preferably 0.9 or less and more preferably 0.7 or
less.
[0076] In view of water absorbability, mechanical strength and heat
resistance, it is preferred that the cellulose hydroxy groups are
partly acylated with a reactive hydrocarbon as mentioned above.
Furthermore, in view of the aforementioned grafting treatment of
cardanol (or a derivative thereof), it is preferred that cellulose
hydroxy groups are appropriately acylated (particularly,
acetylated) before grafting of cardanol (or a derivative thereof).
The number of acyl groups (average value) to be added per glucose
unit of cellulose (or a derivative thereof), in other words, the
number of hydroxy groups acylated (degree of substitution of the
hydroxy group, DS.sub.AC) (average value) is preferably 0.5 or more
in view of obtaining sufficient acylation effect, more preferably
1.0 or more, and further preferably 1.5 or more. Furthermore, in
view of ensuring the sufficient grafting rate (DS.sub.CD) of
cardanol (or a derivative thereof), the degree of substitution of
the hydroxy group, DS.sub.AC by acylation is preferably 2.7 or
less, more preferably 2.5 or less and further preferably 2.2 or
less. The acyl group to be added by acylation is preferably at
least one acyl group selected from an acetyl group, a propionyl
group and a butyryl group. Note that the degree of acetylation is
represented by DS.sub.Ace, the degree of propionation is
represented by DS.sub.Pr, and the degree of butylation is
represented by DS.sub.Bu.
[0077] In the cellulose resin of the exemplary embodiment, in view
of ensuring a sufficient plant utilization ratio, the mass ratio
(plant component ratio) of the sum of a cellulose component and a
cardanol component relative to the total cellulose resin grafted is
preferably 50% or more, and more preferably 60% or more. The
cellulose component herein corresponds to the structure represented
by Formula (1) where hydroxy groups are not acylated or grafted,
whereas the cardanol component corresponds to the structure
represented by Formula (2). On the assumption of these, calculation
is made to obtain the mass ratio.
[0078] To the cellulose resin of the exemplary embodiment described
above, various types of additives usually used in thermoplastic
resins can be applied. For example, if a plasticizer is added,
thermoplasticity and breaking elongation can be more improved.
Examples of such a plasticizer include phthalic esters such as
dibutyl phthalate, diaryl phthalate, diethyl phthalate, dimethyl
phthalate, di-2-methoxyethyl phthalate, ethyl phthalyl ethyl
glycolate and methyl phthalyl ethyl glycolate; tartaric acid esters
such as dibutyl tartrate; adipic acid esters such as dioctyl
adipate and diisononyl adipate; polyhydric alcohol esters such as
triacetin, diacetyl glycerin, tripropionitrile glycerin and
glyceryl monostearate; phosphoric acid esters such as triethyl
phosphate, triphenyl phosphate and tricresyl phosphate; dibasic
fatty acid esters such as dibutyl adipate, dioctyl adipate, dibutyl
azelate, dioctyl azelate and dioctyl sebacate; citric acid esters
such as triethyl citrate, acetyltriethyl citrate and tributyl
acetylcitrate; epoxylated vegetable oils such as epoxylated soybean
oil and epoxylated linseed oil; castor oil and a derivative
thereof; benzoic acid esters such as ethyl O-benzoyl benzoate;
aliphatic dicarboxylic acid esters such as sebacate and azelate;
unsaturated dicarboxylic acid esters such as maleate; and N-ethyl
toluene sulfonamide, triacetin, O-cresyl p-toluenesulfonate and
tripropionin.
[0079] Examples of other plasticizers include cyclohexane
dicarboxylic acid esters such as dihexyl cyclohexanedicarboxylate,
dioctyl cyclohexanedicarboxylate and di-2-methyloctyl
cyclohexanedicarboxylate; trimellitic acid esters such as dihexyl
trimellitate, diethylhexyl trimellitate and dioctyl trimellitate;
and pyromellitic acid esters such as dihexyl pyromellitate,
diethylhexyl pyromellitate and dioctyl pyromellitate.
[0080] The reactive functional group (a carboxylic acid group, a
group derived from a carboxylic acid group, other functional
groups) of such a plasticizer may be reacted with a hydroxy group
or an unsaturated bond of cardanol to allow cardanol to add to a
plasticizer. If such a plasticizer is used, compatibility of the
cellulose resin of the exemplary embodiment and the plasticizer can
be improved. Therefore, the addition effect of the plasticizer can
be more improved.
[0081] To the cellulose resin of the exemplary embodiment, if
necessary, an inorganic or organic granular or fibrous filler can
be added. By adding a filler, strength and rigidity can be more
improved. Examples of the filler include, mineral particles (talc,
mica, baked siliceous earth, kaolin, sericite, bentonite, smectite,
clay, silica, quartz powder, glass beads, glass powder, glass
flake, milled fiber, Wollastonite, etc.), boron-containing
compounds (boron nitride, boron carbonate, titanium boride etc.),
metal carbonates (magnesium carbonate, heavy calcium carbonate,
light calcium carbonate, etc.), metal silicates (calcium silicate,
aluminum silicate, magnesium silicate, magnesium aluminosilicate,
etc.), metal oxides (magnesium oxide etc.), metal hydroxides
(aluminum hydroxide, calcium hydroxide, magnesium hydroxide, etc.),
metal sulfates (calcium sulfate, barium sulfate, etc.), metal
carbides (silicon carbide, aluminum carbide, titanium carbide,
etc.), metal nitrides (aluminum nitride, silicon nitride, titanium
nitride, etc.), white carbon and metal foils. Examples of the
fibrous filler include organic fibers (natural fiber, papers etc.),
inorganic fibers (glass fiber, asbestos fiber, carbon fiber, silica
fiber, silica alumina fiber, Wollastonite, zirconia fiber,
potassium titanate fiber etc.) and metal fibers. These fillers can
be used singly or in combination of two or more types.
[0082] To the cellulose resin of the exemplary embodiment, if
necessary, a flame retardant can be added. By adding a flame
retardant, flame resistance can be imparted. Examples of the flame
retardant include metal hydrates such as magnesium hydroxide,
aluminum hydroxide and hydrotalcite, basic magnesium carbonate,
calcium carbonate, silica, alumina, talc, clay, zeolite,
bromine-based flame retardant, antimony trioxide, phosphoric acid
based flame retardant (aromatic phosphate, aromatic condensed
phosphate, etc.), compounds containing phosphorus and nitrogen
(phosphazene compound), etc. These flame retardants can be used
singly or in combination with two or more types.
[0083] Furthermore, as the flame retardant, a reaction product
between a phosphorus oxide, a phosphoric acid or a derivative of
each of these and cardanol, and a polymers of the reactant can be
used. If such a flame retardant is used, the interaction between
the cellulose resin of the exemplary embodiment and a flame
retardant is enhanced, excellent flame-retardant effect can be
obtained. Examples of such a flame retardant include a reaction
product between phosphorus oxide (P.sub.20.sub.5) or phosphoric
acid (H.sub.3PO.sub.4) and a hydroxy group of cardanol, and a
polymer obtained by adding hexamethylene tetramine to the reactant
followed by polymerizing.
[0084] To the cellulose resin of the exemplary embodiment, if
necessary, a shock resistance improver can be added. By adding a
shock resistance improver, shock resistance can be improved.
Examples of the shock resistance improver include a rubber
component and a silicone compound. Examples of the rubber component
include a natural rubber, epoxylated natural rubber and synthesized
rubber. Furthermore, examples of the silicone compound include
organic polysiloxane formed by polymerization of alkyl siloxane,
alkyl phenyl siloxane, etc., and modified silicone compounds
obtained by modifying a side chain or an end of an organic
polysiloxane as mentioned above with polyether, methylstyryl,
alkyl, higher fatty acid ester, alkoxy, fluorine, an amino group,
an epoxy group, a carboxyl group, a carbinol group, a methacryl
group, a mercapto group, a phenol group etc. These shock resistance
improvers can be used singly or in combination of two or more
types.
[0085] As the silicone compound, a modified silicone compound
(modified polysiloxane compound) is preferred. As the modified
silicone compound, a modified polydimethyl siloxane is preferred,
which has a structure having a main chain constituted of dimethyl
siloxane repeat units and a side chain or a terminal methyl group
partly substituted with an organic substituent containing at least
one group selected from an amino group, an epoxy group, a carbinol
group, a phenol group, a mercapto group, a carboxyl group, a
methacryl group, a long-chain alkyl group, an aralkyl group, a
phenyl group, a phenoxy group, an alkyl phenoxy group, a long-chain
fatty acid ester group, a long-chain fatty acid amide group and a
polyether group. The modified silicone compound, because of the
presence of such an organic substituent, is improved in affinity
for the aforementioned cardanol-added cellulose resin and
dispersibility in the cellulose resin is improved. Consequently, a
resin composition excellent in shock resistance can be
obtained.
[0086] As such a modified silicone compound, a modified silicone
compound produced in accordance with a conventional method or a
commercially available product can be used.
[0087] Examples of the organic substituent contained in the
modified silicone compound include the organic substituents
represented by the following formulas (3) to (21):
##STR00003## ##STR00004##
where a and b each represent an integer of 1 to 50.
[0088] In the aforementioned formulas, R.sub.1 to R.sub.10,
R.sub.12 to R.sub.15, R.sub.19 and R.sub.21 each represent a
divalent organic group. Examples of the divalent organic group
include alkylene groups such as a methylene group, an ethylene
group, a propylene group and a butylene group; alkyl arylene groups
such as a phenylene group and a tolylene group; oxyalkylene groups
and polyoxyalkylene groups such as
--(CH.sub.2--CH.sub.2--O).sub.c-- (c represents an integer from 1
to 50), --[CH.sub.2--CH(CH.sub.3)--O].sub.d-- (d represents an
integer from 1 to 50), and --(CH.sub.2).sub.e--NHCO-- (e represents
an integer from 1 to 8). Of these, an alkylene group is preferable
and particularly, an ethylene group and a propylene group are
preferable.
[0089] In the aforementioned formulas, R.sub.11, R.sub.16 to
R.sub.18, R.sub.20 and R.sub.22 each represent an alkyl group
having 1 to 20 carbon atoms. Examples of the alkyl group include a
methyl group, an ethyl group, a propyl group, a butyl group, a
pentyl group, a hexyl group, a heptyl group, an octyl group, a
nonyl group, a decyl group, an undecyl group, a dodecyl group, a
tridecyl group, a tetradecyl group and a pentadecyl group.
Furthermore, the structures of the above alkyl groups may have one
or more unsaturated bonds.
[0090] The total average content of organic substituents in a
modified silicone compound desirably falls within the range where
the modified silicone having an appropriate particle diameter (for
example, 0.1 .mu.m or more and 100 .mu.m or less) can be dispersed
in a matrix, i.e., a cardanol-added cellulose resin, during a
process for producing a cellulose resin composition. If a modified
silicone compound having an appropriate particle diameter is
dispersed in a cardanol-added cellulose resin, stress concentration
on the periphery of a silicone region having a low elastic modulus
effectively occurs. As a result, a resin compact having excellent
shock resistance can be obtained. The total average content of such
organic substituents is preferably 0.01% by mass or more and more
preferably 0.1% by mass or more, and also preferably 70% by mass or
less and more preferably 50% by mass or less. If an organic
substituent is contained appropriately, the modified silicone
compound can be improved in affinity for a cellulose resin, the
modified silicone compound having an appropriate particle diameter
can be dispersed in a cardanol-added cellulose resin, and further
bleed out due to separation of the modified silicone compound in a
molding can be suppressed. If the total average content of the
organic substituents is excessively low, it becomes difficult to
disperse a modified silicone compound having an appropriate
particle diameter in a cardanol-added cellulose resin.
[0091] If an organic substituent of the modified polydimethyl
siloxane compound is an amino group, an epoxy group, a carbinol
group, a phenol group, a mercapto group, a carboxyl group or a
methacryl group, the average content of the organic substituent in
the modified polydimethyl siloxane compound can be obtained by the
following Expression (I).
Organic substituent average content (%)=(organic substituent
formula-weight/organic substituent equivalent).times.100 (I)
[0092] In the Expression (I), the organic substituent equivalent is
an average mass of a modified silicone compound per organic
substituent (1 mole).
[0093] When the organic substituent of the modified polydimethyl
siloxane compound is a phenoxy group, an alkylphenoxy group, a
long-chain alkyl group, an aralkyl group, a long-chain fatty acid
ester group or a long-chain fatty acid amide group, the average
content of the organic substituent of the modified polydimethyl
siloxane compound can be obtained from the following Expression
(II).
Organic substituent average content
(%)=x.times.w/[(1.times.x).times.74+x.times.(59+w)].times.100
(II)
[0094] In the Expression (II), x is an average molar fraction of
the organic substituent-containing a siloxane repeat unit relative
to all siloxane repeat units of the modified polydimethyl siloxane
compound; and w is the formula weight of the organic
substituent.
[0095] In the case where the organic substituent of the modified
polydimethyl siloxane compound is a phenyl group, the average
content of the phenyl group in the modified polydimethyl siloxane
compound can be obtained by the following Expression (III).
Phenyl group average content
(%)=154.times.x/[74.times.(1-x)+198.times.x].times.100 (III)
[0096] In the Expression (III), x is an average molar fraction of
the phenyl group-containing siloxane repeat unit relative to all
siloxane repeat units in the modified polydimethyl siloxane
compound (A).
[0097] In the case where the organic substituent of the modified
polydimethyl siloxane compound is a polyether group, the average
content of the polyether group in the modified polydimethyl
siloxane compound can be obtained by the following Expression
(IV).
Polyether group average content (%)=HLB value/20.times.100 (IV)
[0098] In the Expression (IV), the HLB value represents the degree
of affinity of a surfactant for water and oil, and is defined by
the following Expression (V) based on the Griffin Act.
HLB value=20.times.(sum of formula weights of hydrophilic
moieties/molecular weight) (V)
[0099] To the cellulose resin of the exemplary embodiment, two or
more modified silicone compounds having different affinities to the
resin may be added. In this case, dispersibility of a relative
low-affinity modified silicone compound (A1) is improved by a
relative high-affinity modified silicone compound (A2) to obtain a
cellulose resin composition having even more excellent shock
resistance. The total average content of an organic substituent of
the relatively low-affinity modified silicone compound (A1) is
preferably 0.01% by mass or more and more preferably 0.1% by mass
or more and also preferably 15% by mass or less and more preferably
10% by mass or less. The total average content of an organic
substituent of the relatively high-affinity modified silicone
compound (A2) is preferably 15% by mass or more and more preferably
20% by mass or more and also preferably 90% by mass or less.
[0100] The blending ratio (mass ratio) of the modified silicone
compound (A1) to the modified silicone compound (A2) can be set to
fall within the range of 10/90 to 90/10.
[0101] In a modified silicone compound, dimethyl siloxane repeat
units and organic substituent-containing siloxane repeat units each
of which may be homologously and continuously connected,
alternately connected or connected at random. A modified silicone
compound may have a branched structure.
[0102] The number average molecular weight of a modified silicone
compound is preferably 900 or more and more preferably 1000 or
more, and also preferably 1000000 or less, more preferably 300000
or less and further preferably 100000 or less. If the molecular
weight of a modified silicone compound is sufficiently large, loss
by vaporization can be suppressed in kneading with a melted
cellulose resin during a process for producing a cardanol-added
cellulose resin compound. Furthermore, if the molecular weight of a
modified silicone compound is appropriate (not excessively large),
a uniform molding having good dispersibility can be obtained.
[0103] As the number average molecular weight, a value (calibrated
by a polystyrene standard sample) obtained by measuring a 0.1%
chloroform solution of a sample by GPC can be employed.
[0104] The addition amount of such a modified silicone compound is
preferably, in view of obtaining sufficient addition effect, 1% by
mass or more relative to the total cellulose resin composition
(particularly, the sum of the cellulose resin and the modified
silicone compound) and more preferably 2% by mass or more. In view
of sufficiently ensuring properties of a cellulose resin such as
strength and suppressing bleed out, the addition amount of a
modified silicone compound is preferably 20% by mass or less and
more preferably 10% by mass or less.
[0105] By adding such a modified silicone compound to a cellulose
resin, the modified silicone compound having an appropriate
particle diameter (for example, 0.1 to 100 .mu.m) can be dispersed
in the resin and the shock resistance of a resin composition can be
improved.
[0106] As the shock resistance improver, a cardanol polymer
containing cardanol as a main component may be used. Such a shock
resistance improver has excellent compatibility with the cellulose
resin of the exemplary embodiment and therefore a higher shock
resistance improving effect can be obtained. Specific examples
thereof include a cardanol polymer obtained by adding formaldehyde
to cardanol and reacting this mixture with an unsaturated bond in
the straight-chain hydrocarbon of cardanol; and a cardanol polymer
obtained by adding a catalyst such as sulfuric acid, phosphoric
acid or diethoxytrifluoroboron and reacting unsaturated bonds of
the straight-chain hydrocarbon of cardanol with each other.
[0107] To the cellulose resin of the exemplary embodiment, if
necessary, additives such as a colorant, an antioxidant and a heat
stabilizer may be added as long as they are applied to conventional
resin compositions.
[0108] To the cellulose resin of the exemplary embodiment, if
necessary, a general thermoplastic resin may be added.
[0109] Particularly, by adding a thermoplastic resin having
excellent flexibility such as a thermoplastic polyurethane
elastomer (TPU), shock resistance can be improved. The addition
amount of such a thermoplastic resin (particularly, TPU) is, in
view of obtaining sufficient addition effect, preferably 1% by mass
or more and more preferably 5% by mass or more relative to the
total composition containing the cellulose resin of the exemplary
embodiment (particularly, to the total amount of the cellulose
resin and the thermoplastic resin (particularly, TPU)). In view of
ensuring the properties of a cellulose resin such as strength and
suppressing bleed out, the addition amount of thermoplastic resin
is preferably 20% by mass or less and more preferably 15% by mass
or less.
[0110] The thermoplastic polyurethane elastomer (TPU) suitable for
improving shock resistance that can be used includes a polyurethane
elastomer prepared by from a polyol, a diisocyanate and a chain
extender.
[0111] Examples of the polyol include polyester polyol, polyester
ether polyol, polycarbonate polyol and polyether polyol.
[0112] Examples of the polyester polyol include a polyester polyol
obtained by a dehydration condensation reaction between a
polyvalent carboxylic acid such as an aliphatic dicarboxylic acid
(succinic acid, adipic acid, sebacic acid, azelaic acid, etc.), an
aromatic dicarboxylic acid (phthalic acid, terephthalic acid,
isophthalic acid, naphthalene dicarboxylic acid, etc.), an
alicyclic dicarboxylic acid (hexahydrophthalic acid,
hexahydroterephthalic acid, hexahydroisophthalic acid, etc.), or an
acid ester or an acid anhydride of each of these, and a polyol such
as ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,
1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane
diol, 3-methyl-1,5-pentane diol, neopentyl glycol, 1,3-octane diol,
1,9-nonane diol, or a mixture of these; and a polylactone diol
obtained by ring-opening polymerization of a lactone monomer such
as .epsilon.-caprolactone.
[0113] Examples of the polyester ether polyol include a compound
obtained by a dehydration condensation reaction between a
polyvalent carboxylic acid such as an aliphatic dicarboxylic acid
(succinic acid, adipic acid, sebacic acid, azelaic acid, etc.), an
aromatic dicarboxylic acid (phthalic acid, terephthalic acid,
isophthalic acid, naphthalene dicarboxylic acid, etc.), an
alicyclic dicarboxylic acid (hexahydrophthalic acid,
hexahydroterephthalic acid, hexahydroisophthalic acid, etc.), or an
acid ester or an acid anhydride of each of these, and a glycol such
as diethylene glycol or an alkylene oxide adduct (propylene oxide
adduct etc.) or a mixture of these.
[0114] Examples of the polycarbonate polyol include a polycarbonate
polyol obtained by reacting one or two or more polyols such as
ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,
1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane
diol, 3-methyl-1,5-pentane diol, neopentyl glycol, 1,8-octane diol,
1,9-nonane diol and diethylene glycol with diethylene carbonate,
dimethyl carbonate, diethyl carbonate, etc.; and further may
include a copolymer of a polycaprolactone polyol (PCL) and a
polyhexamethylene carbonate (PHL).
[0115] Examples of the polyether polyol include a polyethylene
glycol, polypropylene glycol and polytetramethylene ether glycol,
each of which is obtained by polymerizing respective cyclic ethers:
ethylene oxide, propylene oxide and tetrahydrofuran; and
copolyethers of these.
[0116] Examples of the diisocyanate to be used in formation of TPU
include tolylene diisocyanate (TDI), 4,4'-diphenylmethane
diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine
diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone
diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated XDI,
triisocyanate, tetramethyl xylene diisocyanate (TMXDI),
1,6,11-undecane triisocyanate, 1,8-diisocyanatemethyl octane,
lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate,
bicycloheptane triisocyanate and dicyclohexyl methane diisocyanate
(hydrogenated MDI; HMDI). Of these, 4,4'-diphenylmethane
diisocyanate (MDI) and 1,6-hexamethylene diisocyanate (HDI) are
preferably used.
[0117] Examples of the chain extender to be used in formation of
TPU, a low-molecular weight polyol can be used. Examples of the
low-molecular weight polyol include aliphatic polyols such as
ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,
1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane
diol, 3-methyl-1,5-pentane diol, neopentyl glycol, 1,8-octane diol,
1,9-nonane diol, diethylene glycol and 1,4-cyclohexane dimethanol
and glycerin; and aromatic glycols such as 1,4-dimethylolbenzene,
bisphenol A and ethylene oxide or a propylene oxide adduct of
bisphenol A.
[0118] When a silicone compound is copolymerized with a
thermoplastic polyurethane elastomer (TPU) obtained from these
materials, further excellent shock resistance can be obtained.
[0119] These thermoplastic polyurethane elastomers (TPU) may be
used singly or in combination.
[0120] A method for producing a resin composition containing the
cellulose resin of the exemplary embodiment, additives and a
thermoplastic resin, is not particularly limited. For example, the
resin composition can be produced by melting and mixing additives
and the cellulose resin manually by handmixing or by use of a known
mixer such as a tumbler mixer, a ribbon blender, a single-axial or
a multiaxial mixing extruder, and a compounding apparatus such as a
kneader and kneading roll and, if necessary, granulating the
mixture into an appropriate shape. In another preferable process,
additives dispersed in solvent such as an organic solvent and a
resin are mixed and furthermore, if necessary, a coagulation
solvent is added to obtain a mixed composition of the additives and
the resin and thereafter, the solvent is evaporated.
[0121] The cellulose resin according to the exemplary embodiments
mentioned above can be used as a base resin for a molding material.
The molding material formed of a resin composition containing the
cellulose resin as a base resin is suitable for forming housing
such as packaging for an electronic device.
[0122] The base resin herein refers to a main component of a
composition and means that other components may be contained as
long as the components do not prevent the function of the main
component. The content rate of the main component is not
particularly limited; however, the content rate of the main
component in a composition is preferably 50% by mass or more, more
preferably 70% by mass or more, further preferably 80% by mass or
more and particularly preferably 90% by mass or more.
EXAMPLES
[0123] The present invention will be more specifically described by
way of examples below.
Synthesis Example 1
Cardanol Derivative 1 (Preparation of Chloridized and Succinic
Acid-Modified Cardanol)
[0124] Hydrogenated cardanol (m-n-pentadecylphenol manufactured by
ACROS Organics), in which an unsaturated bond(s) of the
straight-chain hydrocarbon moiety of cardanol are hydrogenated, was
used as a raw material. When the hydrogenated cardanol was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), no unsaturated bond was detected. Thus, it was confirmed
that a hydrogenation rate is at least 90% by mole or more. The
phenolic hydroxy group of the cardanol was reacted with succinic
anhydride to add a carboxyl group to obtain carboxylated and
hydrogenated cardanol. Next, the carboxyl group was converted into
an acid chloride group by chloridizing it with oxalyl chloride to
obtain chloridized and hydrogenated cardanol. More specifically,
the chloridized and hydrogenated cardanol was prepared in
accordance with the following procedure.
[0125] First, succinic anhydride (33 g (0.33 mol)) was dissolved in
dehydrated chloroform (250 mL). To this, dehydrated pyridine (5.0
mL (0.062 mol)) and a raw material, i.e., hydrogenated cardanol (50
g (0.16 mol)) were added. The reaction solution was heated to
reflux under a nitrogen atmosphere at 70.degree. C. for 24 hours,
cooled to room temperature. Thereafter, a crystal of succinic
anhydride precipitated was separated by filtration. The chloroform
solution filtrated was washed twice with 0.1 mol/L hydrochloric
acid (250 mL) and further washed twice with water (250 mL). After
washing, the chloroform solution was dehydrated with magnesium
sulfate and magnesium sulfate was separated by filtration and
chloroform was distillated away under reduced pressure to obtain a
brown solid substance of carboxylated and hydrogenated cardanol (60
g (0.15 mol)).
[0126] The resultant carboxylated and hydrogenated cardanol (50 g
(0.12 mol) was dissolved in dehydrated chloroform (250 mL). To
this, oxalyl chloride (24 g (0.19 mol)) and N,N-dimethylformamide
(0.25 mL (3.2 mmol)) were added. The reaction solution was stirred
at room temperature for 72 hours. Chloroform, excessive oxalyl
chloride and N,N-dimethylformamide were distillated away under
reduced pressure to obtain chloridized and hydrogenated cardanol
(52 g (0.12 mol).
Synthesis Example 2
Cardanol Derivative 2 (Preparation of Chloridized and
Monochloroaceti Acid-Modified Cardanol)
[0127] Hydrogenated cardanol (m-n-pentadecylphenol manufactured by
ACROS Organics), in which an unsaturated bond(s) of the
straight-chain hydrocarbon moiety of cardanol are hydrogenated, was
used as a raw material. The phenolic hydroxy group of the cardanol
was reacted with monochloroacetic acid to add a carboxyl group to
obtain carboxylated and hydrogenated cardanol. Next, the carboxyl
group was converted into an acid chloride group by chloridizing it
with oxalyl chloride to obtain chloridized and hydrogenated
cardanol. More specifically, the chloridized and hydrogenated
cardanol was prepared in accordance with the following
procedure.
[0128] First, hydrogenated cardanol (80 g (0.26 mol)) was dissolved
in methanol (120 mL). To this, an aqueous solution of sodium
hydroxide (64 g (1.6 mol)) dissolved in distilled water (40 mL) was
added. Thereafter, at room temperature, a solution of monochloro
acetic acid (66 g (0.70 mol)) (manufactured by Kanto Chemical Co.,
Inc.) dissolved in methanol (50 mL) was added dropwise. After
completion of the dropwise addition, the reaction solution was
continuously stirred while refluxing at 73.degree. C. for 4 hours.
The reaction solution was cooled to room temperature and the
reaction mixture was acidified with a diluted hydrochloric acid
until pH became 1. To this, methanol (250 mL) and diethyl ether
(500 mL) and further distilled water (200 mL) were added. The
resultant water layer was separated by a separating funnel and
discarded. The ether layer was washed twice with distilled water
(400 mL). To the ether layer, magnesium anhydride was added to dry
the ether layer and then separated by filtration. The filtrate
(ether layer) was concentrated by an evaporator (90.degree. C./3
mmHg) under reduced pressure to obtain a yellow brown powdery crude
product as the residue. The crude product was recrystallized from
n-hexane and dried under vacuum to obtain white powder of
carboxylated and hydrogenated cardanol (46 g (0.12 mol)).
[0129] The resultant carboxylated and hydrogenated cardanol (46 g
(0.12 mol)) was dissolved in dehydrated chloroform (250 mL). To
this, oxalyl chloride (24 g (0.19 mol)) and N,N-dimethylformamide
(0.25 mL (3.2 mmol) were added. The mixture was stirred at room
temperature for 72 hours. Chloroform, excessive oxalyl chloride and
N,N-dimethylformamide were distillated away under reduced pressure
to obtain chloridized and hydrogenated cardanol (48 g (0.13
mol)).
Synthesis Example 3
Preparation of Biphenylacetyl Chloride
[0130] Biphenylacetic acid (6.0 g (0.028 mol)) manufactured by
Sigma-Aldrich Co. LLC was dissolved in dehydrated chloroform (60
ml). To this, oxalyl chloride (3.7 g (0.029 mol)) and
N,N-dimethylformamide (0.04 ml (0.51 mmol)) were added. The mixture
was stirred at room temperature for 72 hours. Chloroform, excessive
oxalyl chloride and N,N-dimethylformamide were distillated away
under reduced pressure to obtain biphenylacetyl chloride (6.5 g
(0.028 mol)).
Example 1
[0131] The chloridized and hydrogenated cardanol (cardanol
derivative 1) prepared in Synthesis Example 1 was allowed to bind
to cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, the grafted cellulose acetate was prepared in
accordance with the following procedure.
[0132] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (46 g
(0.11 mol)) prepared in Synthesis Example 1 was added. The reaction
solution was heated to reflux at 100.degree. C. for 6 hours. The
reaction solution was slowly added dropwise to methanol (3 L) while
stirring to allow reprecipitation. The resultant solid substance
was separated by filtration, dried overnight in the air and further
dried under vacuum at 105.degree. C. for 5 hours to obtain grafted
cellulose acetate (20 g).
[0133] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.90.
[0134] Furthermore, the sample was evaluated in the following
procedure. The results are shown in Table 1A.
[Evaluation of Thermoplasticity (Press Moldability)]
[0135] Press molding was performed in the following conditions to
obtain a compact. At that time, moldability was evaluated in
accordance with the following criteria.
(Molding Conditions)
[0136] Temperature: 170.degree. C., Time: 2 minutes, Pressure: 100
kgf (9.8.times.10.sup.2 N),
[0137] Size of compact: Thickness: 2 mm, Width: 13 mm, Length: 80
mm.
(Evaluation criteria)
[0138] .largecircle.: Good, .DELTA.: not good (void, sink mark or
partial uncharged portion was observed), x: cannot be molded.
[Measurement of Glass Transition Temperature (Heat Resistance
Evaluation)]
[0139] Glass transition temperature was measured by DSC (product
name: DSC6200, manufactured by Seiko Instruments Inc.).
[Bending Test]
[0140] The compact obtained by the aforementioned molding process
was subjected to a bending test in accordance with JIS K7171.
[Tensile Test]
[0141] A solution of a sample (2 g) dissolved in chloroform (20 mL)
was prepared. The solution was subjected to casting and a film of
10 mm in width, 60 mm in length and 0.2 mm in thickness was
prepared by cutting out by a cutter knife. The film was subjected
to a tensile test in accordance with JIS K7127.
[Measurement of Water Absorption Rate]
[0142] Water absorption rate was obtained by measurement in
accordance with JIS K7209. More specifically, the compact was
soaked in pure water for 24 hours at normal temperature. An
increase of weight at this time was measured to obtain a weight
increase rate.
[Determination of Plant-Component Ratio]
[0143] A cellulose component and a cardanol component were regarded
as plant components. The total content rate (% by mass) of the
plant components relative to the whole sample was obtained.
Assuming that the cellulose component herein corresponds to that
having a structure represented by Formula (1) above in which a
hydroxy group is not acylated or grafted, and that the cardanol
component corresponds to that having a structure represented by
Formula (2) above, calculation was made.
Example 2
[0144] The chloridized and hydrogenated cardanol (cardanol
derivative 1) prepared in Synthesis Example 1 was allowed to bind
to cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, the grafted cellulose acetate was prepared in
accordance with the following procedure.
[0145] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (23 g
(0.054 mol)) prepared in Synthesis Example 1 was added. The
reaction solution was heated to reflux at 100.degree. C. for 6
hours. The reaction solution was slowly added dropwise to methanol
(3 L) while stirring to allow reprecipitation. The resultant solid
substance was separated by filtration, dried overnight in the air
and further dried under vacuum at 105.degree. C. for 5 hours to
obtain grafted cellulose acetate (16 g).
[0146] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.55.
[0147] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1A.
Example 3
[0148] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 was allowed to bind
to cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, the grafted cellulose acetate was prepared in
accordance with the following procedure.
[0149] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (14 g
(0.037 mol)) prepared in Synthesis Example 2 was added. The
reaction solution was heated to reflux at 100.degree. C. for 3
hours. The reaction solution was slowly added dropwise to methanol
(3 L) while stirring to allow reprecipitation. The resultant solid
substance was separated by filtration, dried overnight in the air
and further dried under vacuum at 105.degree. C. for 5 hours to
obtain grafted cellulose acetate (15 g).
[0150] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.55.
[0151] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1A.
Example 4
[0152] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 was allowed to bind
to cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 3 except that the supply amount of
the chloridized and hydrogenated cardanol was changed to 21 g
(0.054 mol) to obtain grafted cellulose acetate (19 g).
[0153] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.80.
[0154] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1A.
Example 5
[0155] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 was allowed to bind
to cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 3 except that the supply amount of
chloridized and hydrogenated cardanol was changed to 12 g (0.031
mol) to obtain grafted cellulose acetate (14 g).
[0156] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.44.
[0157] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1A.
Example 6
[0158] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 was allowed to bind
to cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 3 except that the supply amount of
the chloridized and hydrogenated cardanol was changed to 6.9 g
(0.018 mol) to obtain grafted cellulose acetate (13 g).
[0159] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.30.
[0160] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1A.
Example 7
[0161] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and benzoyl chloride
(BC) as a reactive hydrocarbon were allowed to bind to cellulose
acetate (trade name: LM-80, manufactured by Daicel Chemical
Industries, Ltd., the number of acetic acid molecules added to a
single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, the grafted cellulose acetate was prepared in
accordance with the following procedure.
[0162] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (4.1
g (0.011 mol)) prepared in Synthesis Example 2 and benzoyl chloride
(BC) (2.8 g (0.020 mol)) manufactured by Tokyo Kasei Kogyo Co.,
Ltd. was added. The reaction solution was heated to reflux at
100.degree. C. for 5 hours. The reaction solution was slowly added
dropwise to methanol (3 L) while stirring to allow reprecipitation.
The resultant solid substance was separated by filtration, dried
overnight in the air and further dried under vacuum at 105.degree.
C. for 5 hours to obtain grafted cellulose acetate (13 g).
[0163] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.30 and DS.sub.BC was 0.14.
[0164] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 8
[0165] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and benzoyl chloride
(BC) as a reactive hydrocarbon were allowed to bind to cellulose
acetate (trade name: LM-80, manufactured by Daicel Chemical
Industries, Ltd., the number of acetic acid molecules added to a
single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 7 except that the supply amount of
the chloridized and hydrogenated cardanol was changed to 3.1 g
(0.008 mol) and the supply amount of benzoyl chloride was changed
to 8.4 g (0.060 mol) to obtain grafted cellulose acetate (14
g).
[0166] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.22 and DS.sub.BC was 0.27.
[0167] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 9
[0168] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and benzoyl chloride
(BC) as a reactive hydrocarbon were allowed to bind to cellulose
acetate (trade name: LM-80, manufactured by Daicel Chemical
Industries, Ltd., the number of acetic acid molecules added to a
single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 7 except that the supply amount of
the chloridized and hydrogenated cardanol was changed to 7.6 g
(0.020 mol) and the supply amount of benzoyl chloride was changed
to 8.4 g (0.060 mol) to obtain grafted cellulose acetate (16
g).
[0169] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.44 and DS.sub.BC was 0.22.
[0170] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 10
[0171] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and benzoyl chloride
(BC) as a reactive hydrocarbon were allowed to bind to cellulose
acetate (trade name: LM-80, manufactured by Daicel Chemical
Industries, Ltd., the number of acetic acid molecules added to a
single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 7 except that the supply amount of
the chloridized and hydrogenated cardanol was changed to 4.1 g
(0.011 mol) and the supply amount of benzoyl chloride was changed
to 28.1 g (0.20 mol) to obtain grafted cellulose acetate (15
g).
[0172] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.24 and DS.sub.BC was 0.42.
[0173] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 11
[0174] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and benzoyl chloride
(BC) as a reactive hydrocarbon were allowed to bind to cellulose
acetate (trade name: LM-80, manufactured by Daicel Chemical
Industries, Ltd., the number of acetic acid molecules added to a
single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 7 except that the supply amount of
the chloridized and hydrogenated cardanol was changed to 4.6 g
(0.012 mol) and the supply amount of benzoyl chloride was changed
to 1.1 g (0.008 mol) to obtain grafted cellulose acetate (14
g).
[0175] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.30 and DS.sub.BC was 0.07.
[0176] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 12
[0177] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and benzoyl chloride
(BC) as a reactive hydrocarbon were allowed to bind to cellulose
acetate (trade name: LM-80, manufactured by Daicel Chemical
Industries, Ltd., the number of acetic acid molecules added to a
single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 7 except that the supply amount of
the chloridized and hydrogenated cardanol was changed to 1.5 g
(0.004 mol) and the supply amount of benzoyl chloride was changed
to 2.2 g (0.016 mol) to obtain grafted cellulose acetate (12
g).
[0178] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.08 and DS.sub.BC was 0.16.
[0179] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 13
[0180] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and biphenylacetyl
chloride (BAA) prepared in Synthesis Example 3 as a reactive
hydrocarbon were allowed to bind to cellulose acetate (trade name:
LM-80, manufactured by Daicel Chemical Industries, Ltd., the number
of acetic acid molecules added to a single glucose unit of
cellulose (degree of acetylation: DS.sub.Ace)=2.1) to obtain
grafted cellulose acetate. More specifically, the grafted cellulose
acetate was prepared in accordance with the following
procedure.
[0181] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (7.0
g (0.018 mol)) prepared in Synthesis Example 2 and biphenylacetyl
chloride (BAA) (1.5 g (0.0065 mol)) prepared in Synthesis Example 3
was added. The reaction solution was heated to reflux at
100.degree. C. for 5 hours. The reaction solution was slowly added
dropwise to methanol (3 L) while stirring to allow reprecipitation.
The resultant solid substance was separated by filtration, dried
overnight in the air and further dried under vacuum at 105.degree.
C. for 5 hours to obtain grafted cellulose acetate (13 g).
[0182] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.27 and DS.sub.BAA was 0.15.
[0183] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 14
[0184] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and biphenylacetyl
chloride (BAA) prepared in Synthesis Example 3 as a reactive
hydrocarbon were allowed to bind to cellulose acetate (trade name:
LM-80, manufactured by Daicel Chemical Industries, Ltd., the number
of acetic acid molecules added to a single glucose unit of
cellulose (degree of acetylation: DS.sub.Ace)=2.1) to obtain
grafted cellulose acetate. More specifically, preparation was made
in accordance with the same content and manner as in Example 13
except that the supply amount of the chloridized and hydrogenated
cardanol was changed to 12.2 g (0.032 mol) and the supply amount of
biphenylacetyl chloride was changed to 4.6 g (0.020 mol) to obtain
grafted cellulose acetate (14 g).
[0185] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.40 and DS.sub.BAA was 0.40.
[0186] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 15
[0187] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and biphenylacetyl
chloride (BAA) prepared in Synthesis Example 3 as a reactive
hydrocarbon were allowed to bind to cellulose acetate (trade name:
LM-80, manufactured by Daicel Chemical Industries, Ltd., the number
of acetic acid molecules added to a single glucose unit of
cellulose (degree of acetylation: DS.sub.Ace)=2.1) to obtain
grafted cellulose acetate. More specifically, preparation was made
in accordance with the same content and manner as in Example 13
except that the supply amount of the chloridized and hydrogenated
cardanol was changed to 15.2 g (0.040 mol) and the supply amount of
biphenylacetyl chloride was changed to 3.2 g (0.014 mol) to obtain
grafted cellulose acetate (14 g).
[0188] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.55 and DS.sub.BAA was 0.28.
[0189] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 16
[0190] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and biphenylacetyl
chloride (BAA) prepared in Synthesis Example 3 as a reactive
hydrocarbon were allowed to bind to cellulose acetate (trade name:
LM-80, manufactured by Daicel Chemical Industries, Ltd., the number
of acetic acid molecules added to a single glucose unit of
cellulose (degree of acetylation: DS.sub.Ace)=2.1) to obtain
grafted cellulose acetate. More specifically, preparation was made
in accordance with the same content and manner as in Example 13
except that the supply amount of the chloridized and hydrogenated
cardanol was changed to 7.6 g (0.020 mol) and the supply amount of
biphenylacetyl chloride was changed to 7.4 g (0.032 mol) to obtain
grafted cellulose acetate (14 g).
[0191] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.30 and DS.sub.BAA was 0.52.
[0192] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1B.
Example 17
[0193] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and phenylpropionyl
chloride (PPA) as a reactive hydrocarbon were allowed to bind to
cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, the grafted cellulose acetate was prepared in
accordance with the following procedure.
[0194] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (4.0
g (0.011 mol)) prepared in Synthesis Example 2 and phenylpropionyl
chloride (PPA) (2.0 g (0.012 mol)) manufactured by Tokyo Kasei
Kogyo Co., Ltd. was added. The reaction solution was heated to
reflux at 100.degree. C. for 5 hours. The reaction solution was
slowly added dropwise to methanol (3 L) while stirring to allow
reprecipitation. The resultant solid substance was separated by
filtration, dried overnight in the air and further dried under
vacuum at 105.degree. C. for 5 hours to obtain grafted cellulose
acetate (13 g).
[0195] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.17 and DS.sub.PPA was 0.25.
[0196] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1C.
Example 18
[0197] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and phenylpropionyl
chloride (PPA) as a reactive hydrocarbon were allowed to bind to
cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 17 except that the supply amount
of the chloridized and hydrogenated cardanol was changed to 3.8 g
(0.010 mol) and the supply amount of phenylpropionyl chloride was
changed to 2.7 g (0.016 mol) to obtain grafted cellulose acetate
(14 g).
[0198] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.Cd was 0.13 and DS.sub.PPA was 0.35.
[0199] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1C.
Example 19
[0200] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and
cyclohexanecarboxylic acid chloride (CHC) as a reactive hydrocarbon
were allowed to bind to cellulose acetate (trade name: LM-80,
manufactured by Daicel Chemical Industries, Ltd., the number of
acetic acid molecules added to a single glucose unit of cellulose
(degree of acetylation: DS.sub.Ace)=2.1) to obtain grafted
cellulose acetate. More specifically, the grafted cellulose acetate
was prepared in accordance with the following procedure.
[0201] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (3.7
g (0.0096 mol)) prepared in Synthesis Example 2 and
cyclohexanecarboxylic acid chloride (CHC) (2.5 g (0.017 mol))
manufactured by Sigma-Aldrich Co. LLC was added. The reaction
solution was heated to reflux at 100.degree. C. for 5 hours. The
reaction solution was slowly added dropwise to methanol (3 L) while
stirring to allow reprecipitation. The resultant solid substance
was separated by filtration, dried overnight in the air and further
dried under vacuum at 105.degree. C. for 5 hours to obtain grafted
cellulose acetate (13 g).
[0202] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.20 and DS.sub.cHc was 0.22.
[0203] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1C.
Example 20
[0204] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and biphenylcarbonyl
chloride (BCC) as a reactive hydrocarbon were allowed to bind to
cellulose acetate (trade name: LM-80, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.1) to obtain grafted cellulose acetate. More
specifically, the grafted cellulose acetate was prepared in
accordance with the following procedure.
[0205] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (4.6
g (0.012 mol)) prepared in Synthesis Example 2 and biphenylcarbonyl
chloride (BCC) (13.0 g (0.060 mol)) manufactured by Sigma-Aldrich
Co. LLC was added. The reaction solution was heated to reflux at
100.degree. C. for 5 hours. The reaction solution was slowly added
dropwise to methanol (3 L) while stirring to allow reprecipitation.
The resultant solid substance was separated by filtration, dried
overnight in the air and further dried under vacuum at 105.degree.
C. for 5 hours to obtain grafted cellulose acetate (16 g).
[0206] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.30 and DS.sub.BCC was 0.30.
[0207] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 1C.
Example 21
[0208] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 was allowed to bind
to cellulose acetate (trade name: LM-40, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.4) to obtain grafted cellulose acetate. More
specifically, the grafted cellulose acetate was prepared in
accordance with the following procedure.
[0209] Cellulose acetate (15.8 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (6.8
g (0.018 mol)) prepared in Synthesis Example 2 was added. The
reaction solution was heated to reflux at 100.degree. C. for 5
hours. The reaction solution was slowly added dropwise to methanol
(3 L) while stirring to allow reprecipitation. The resultant solid
substance was separated by filtration, dried overnight in the air
and further dried under vacuum at 105.degree. C. for 5 hours to
obtain grafted cellulose acetate (19 g).
[0210] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.19.
[0211] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 2.
Example 22
[0212] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 was allowed to bind
to cellulose acetate (trade name: LM-40, manufactured by Daicel
Chemical Industries, Ltd., the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=2.4) to obtain grafted cellulose acetate. More
specifically, preparation was made in accordance with the same
content and manner as in Example 22 except that the supply amount
of chloridized and hydrogenated cardanol was changed to 41.2 g
(0.108 mol) to obtain grafted cellulose acetate (25 g).
[0213] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.50.
[0214] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 2.
Example 23
[0215] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 was allowed to bind
to cellulose acetate butyrate (trade name: CAB-381-20, manufactured
by Eastman Chemical Company, the number of acetic acid molecules
added to a single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=1.0; the number of butyric acid molecules added to a
single glucose unit of cellulose (degree of butyration:
DS.sub.Bu)=1.66) to obtain grafted cellulose acetate. More
specifically, the grafted cellulose acetate butyrate was prepared
in accordance with the following procedure.
[0216] Cellulose acetate butyrate (10 g (hydroxy-group amount:
0.011 mol)) was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (2.5 ml (0.018 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (13 g
(0.035 mol)) prepared in Synthesis Example 2 was added. The
reaction solution was heated to reflux at 100.degree. C. for 5
hours. The reaction solution was slowly added dropwise to methanol
(3 L) while stirring to allow reprecipitation. The resultant solid
substance was separated by filtration, dried overnight in the air
and further dried under vacuum at 105.degree. C. for 5 hours to
obtain grafted cellulose acetate butyrate (13 g).
[0217] The obtained sample (grafted cellulose acetate butyrate) was
measured by .sup.1H-NMR (product name: AV-400, 400 MHz,
manufactured by Bruker), and DS.sub.CD was 0.34.
[0218] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 3.
Example 24
[0219] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 was allowed to bind
to cellulose acetate propionate (trade name: CAP-482-20,
manufactured by Eastman Chemical Company, the number of acetic acid
molecules added to a single glucose unit of cellulose (degree of
acetylation: DS.sub.Ace)=0.18; the number of propionic acid
molecules added to a single glucose unit of cellulose (degree of
propionation: DS.sub.Pr)=2.49) to obtain grafted cellulose acetate
propionate. More specifically, the grafted cellulose acetate
propionate was prepared in accordance with the following
procedure.
[0220] Cellulose acetate propionate (10 g (hydroxy-group amount:
0.010 mol)) was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (2.5 ml (0.018 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (13 g
(0.035 mol)) prepared in Synthesis Example 2 was added. The
reaction solution was heated to reflux at 100.degree. C. for 5
hours. The reaction solution was slowly added dropwise to methanol
(3 L) while stirring to allow reprecipitation. The resultant solid
substance was separated by filtration, dried overnight in the air
and further dried under vacuum at 105.degree. C. for 5 hours to
obtain grafted cellulose acetate (13 g).
[0221] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.34.
[0222] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 3.
Example 25
[0223] The chloridized and hydrogenated cardanol (cardanol
derivative 2) prepared in Synthesis Example 2 and benzoyl chloride
(BC) as a reactive hydrocarbon were allowed to bind to cellulose
acetate propionate (trade name: CAP-482-20, manufactured by Eastman
Chemical Company, the number of acetic acid molecules added to a
single glucose unit of cellulose (degree of acetylation:
DS.sub.Ace)=0.18; the number of propionic acid molecules added to a
single glucose unit of cellulose (degree of propionation:
DS.sub.Pr)=2.49) to obtain grafted cellulose acetate propionate.
More specifically, the grafted cellulose acetate propionate was
prepared in accordance with the following procedure.
[0224] Cellulose acetate propionate (10 g (hydroxy-group amount:
0.010 mol)) was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (2.5 ml (0.018 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving the chloridized and hydrogenated cardanol (4.5
g (0.012 mol)) prepared in Synthesis Example 2 and benzoyl chloride
(BC) (2.8 g (0.020 mol)) manufactured by Tokyo Kasei Kogyo Co.,
Ltd. was added. The reaction solution was heated to reflux at
100.degree. C. for 5 hours. The reaction solution was slowly added
dropwise to methanol (3 L) while stirring to allow reprecipitation.
The resultant solid substance was separated by filtration, dried
overnight in the air and further dried under vacuum at 105.degree.
C. for 5 hours to obtain grafted cellulose acetate (13 g).
[0225] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.CD was 0.21 and DS.sub.BC was 0.10.
[0226] Furthermore, the sample was evaluated in the same manner as
in Example 1. The results are shown in Table 3.
Example 26
[0227] Hydrogenated cardanol (m-n-pentadecylphenol manufactured by
ACROS Organics), in which an unsaturated bond(s) of the
straight-chain hydrocarbon moiety of cardanol are hydrogenated, was
used as a raw material. The phenolic hydroxy group of the cardanol
was reacted with monochloroacetic acid to add a carboxyl group to
obtain carboxylated and hydrogenated cardanol. More specifically,
the carboxylated and hydrogenated cardanol was prepared in
accordance with the following procedure.
[0228] First, hydrogenated cardanol (80 g (0.26 mol)) was dissolved
in methanol (120 mL). To this, an aqueous solution dissolving
sodium hydroxide (64 g (1.6 mol)) in distilled water (40 mL) was
added. Thereafter, at room temperature, a solution of monochloro
acetic acid (66 g (0.70 mol)) manufactured by Kanto Chemical Co.,
Inc. dissolved in methanol (50 mL) was added dropwise. After
completion of the dropwise addition, the reaction solution was
continuously stirred while refluxing at 73.degree. C. for 4 hours.
The reaction solution was cooled to room temperature and the
reaction mixture was acidified with a diluted hydrochloric acid
until pH became 1. To this, methanol (250 mL) and diethyl ether
(500 mL) and further distilled water (200 mL) were added. The
resultant water layer was separated by a separating funnel and
discarded. The ether layer was washed twice with distilled water
(400 mL). To the ether layer, magnesium anhydride was added to dry
the ether layer and then separated by filtration. The filtrate
(ether layer) was concentrated by an evaporator (90.degree. C./3
mmHg) under reduced pressure to obtain a yellow brown powdery crude
product as the residue. The crude product was recrystallized from
n-hexane and dried under vacuum to obtain white powder of
carboxylated and hydrogenated cardanol (46 g (0.12 mol)).
[0229] The carboxylated and hydrogenated cardanol thus prepared was
allowed to bind to cellulose (trade name: KC Flock W-50G
manufactured by Nippon Paper Chemicals) to obtain grafted
cellulose. More specifically, the grafted cellulose was prepared in
accordance with the following procedure.
[0230] Cellulose (2.5 g (hydroxy-group amount: 47 mmol)) was
suspended in methanol (100 mL) and stirred for one hour at room
temperature and filtrated by suction. The solid substance separated
by filtration was allowed to swell with dimethylacetamide (DMAc)
(100 mL), stirred one hour at room temperature and filtrated by
suction to remove the solvent. Thereafter, swelling with DMAc and
solvent removal by suction filtration were repeated three times in
the same manner. LiCl (21 g) was dissolved in DMAc (250 mL) and the
DMAc-swollen cellulose previously obtained was mixed and stirred at
room temperature overnight to obtain a cellulose solution. To the
cellulose solution thus obtained, a DMAc solution (20 mL)
dissolving the carboxylated and hydrogenated cardanol (17.3 g (46.5
mmol)), pyridine (11.0 g (140 mmol)) and tosyl chloride (8.8 g (46
mmol)) was added. The reaction solution was reacted by heating at
50.degree. C. for one hour. The reaction solution was added
dropwise to methanol (2L) to allow reprecipitation. The resultant
solid substance was separated by filtration, washed three times
with methanol (500 mL) and dried under vacuum at 105.degree. C. for
5 hours to obtain grafted cellulose (10.4 g). DS.sub.CD was
obtained from the yield, and DS.sub.CD was 1.49. Furthermore, the
sample was evaluated in the same manner as in Example 1. The
results are shown in Table 4.
Comparative Example 1
[0231] The same cellulose acetate before grafting as that used in
Example 1 was used as a comparative sample.
[0232] The cellulose acetate was evaluated in the same manner as in
Example 1. The results are shown in Table 1C.
[0233] Note that the cellulose acetate did not melt even if heated
and did not exhibit thermoplasticity. Furthermore, since the
cellulose acetate could not be molded, a bending test was not
performed.
Comparative Example 2
[0234] To the same cellulose acetate before grafting as that used
in Example 1, triethyl citrate (trade name: Citroflex-2
manufactured by Pfizer Inc.) was added as a plasticizer such that
the content became 45% by mass based on the whole resin
composition. This was mixed by an extruder mixer (HAAKE MiniLab
Rheomex extruder (Model CTW5, Thermo Electron Corp., Waltham,
Mass.)) at a temperature of 200.degree. C. and a screw rotation
speed of 60 rpm to prepare a cellulose acetate resin
composition.
[0235] The resin composition was evaluated in the same manner as in
Example 1. The results are shown in Table 1C.
[0236] Note that when the resin composition was casted, a phase
separation occurred and a uniform film could not be prepared. Thus,
a tensile test was not performed.
Comparative Example 3
[0237] A cellulose acetate resin composition was prepared in
accordance with the same content and manner as in Comparative
Example 2 except that the addition amount of triethyl citrate was
set to 56% by mass based on the whole resin composition.
[0238] The resin composition was evaluated in the same manner as in
Example 1. The results are shown in Table 1C.
[0239] Note that when the resin composition was casted, a phase
separation occurred and a uniform film could not be prepared. Thus,
a tensile test was not performed.
Comparative Example 4
[0240] A cellulose acetate resin composition was prepared in
accordance with the same content and manner as in Comparative
Example 2 except that the addition amount of triethyl citrate was
set to 34% by mass based on the whole resin composition.
[0241] The resin composition was evaluated in the same manner as in
Example 1. The results are shown in Table 1C.
[0242] Note that when the resin composition was casted, a phase
separation occurred and a uniform film could not be prepared. Thus,
a tensile test was not performed.
Comparative Example 5
[0243] Phenylpropionyl chloride (PPA) was used as a reactive
hydrocarbon and allowed to bind to cellulose acetate (trade name:
LM-80, manufactured by Daicel Chemical Industries, Ltd., the number
of acetic acid molecules added to a single glucose unit of
cellulose (degree of acetylation: DS.sub.Ace)=2.1) to obtain
grafted cellulose acetate. More specifically, the grafted cellulose
acetate was prepared in accordance with the following
procedure.
[0244] Cellulose acetate (10 g (hydroxy-group amount: 0.036 mol))
was dissolved in dehydrated dioxane (200 mL). To this,
triethylamine (5.0 ml (0.036 mol)) was added as a reaction catalyst
and an acid trapping agent. To the solution, a dioxane solution
(100 mL) dissolving phenylpropionyl chloride (PPA) (10 g (0.060
mol)) manufactured by Tokyo Kasei Kogyo Co., Ltd., was added. The
reaction solution was heated to reflux at 100.degree. C. for one
hour. The reaction solution was slowly added dropwise to methanol
(3 L) while stirring to allow reprecipitation. The resultant solid
substance was separated by filtration, dried overnight in the air
and further dried under vacuum at 105.degree. C. for 5 hours to
obtain grafted cellulose acetate (12 g).
[0245] The obtained sample (grafted cellulose acetate) was measured
by .sup.1H-NMR (product name: AV-400, 400 MHz, manufactured by
Bruker), and DS.sub.PPA was 0.47.
[0246] The sample was evaluated in the same manner as in Example 1.
The results are shown in Table 1C.
[0247] Note that the cellulose acetate did not melt even if heated
and did not exhibit thermoplasticity. Furthermore, since the
cellulose acetate could not be molded, a bending test was not
performed.
Comparative Example 6
[0248] The same cellulose acetate before grafting (DS.sub.Ace=2.4)
as that used in Example 21 was used as a comparative sample.
[0249] The cellulose acetate was evaluated in the same manner as in
Example 1. The results are shown in Table 2.
[0250] Note that the cellulose acetate did not melt even if heated
and did not exhibit thermoplasticity. Furthermore, since the
cellulose acetate could not be molded, a bending test was not
performed.
Comparative Example 7
[0251] To the same cellulose acetate (DS.sub.Ace=2.4) before
grafting as that used in Example 21, triethyl citrate (trade name:
Citroflex-2 manufactured by Pfizer Inc.) was added as a plasticizer
such that the content became 20% by mass based on the whole resin
composition. This was mixed by an extruder mixer (HAAKE MiniLab
Rheomex extruder (Model CTW5, Thermo Electron Corp., Waltham,
Mass.)) at a temperature of 190.degree. C. and a screw rotation
speed of 60 rpm) to prepare a cellulose acetate resin
composition.
[0252] The resin composition was evaluated in the same manner as in
Example 1. The results are shown in Table 2.
[0253] Note that when the resin composition was casted, a phase
separation occurred and a uniform film could not be prepared. Thus,
a tensile test was not performed.
Comparative Example 8
[0254] A cellulose acetate resin composition was prepared in
accordance with the same content and manner as in Comparative
Example 7 except that the addition amount of triethyl citrate was
set to 40% by mass based on the whole resin composition.
[0255] The resin composition was evaluated in the same manner as in
Example 1. The results are shown in Table 2.
[0256] Note that when the resin composition was casted, a phase
separation occurred and a uniform film could not be prepared. Thus,
a tensile test was not performed.
Comparative Examples 9 and 10
[0257] The same cellulose acetate butyrate and cellulose acetate
propionate before grafting as those that used in Examples 23 and 24
were used as comparative samples respectively.
[0258] The cellulose acetate butyrate and cellulose acetate
propionate were evaluated in the same manner as in Example 1. The
results are shown in Table 3.
[0259] Note that the cellulose acetate butyrate and cellulose
acetate propionate melted when heated. They had thermoplasticity;
however, melt viscosity was extremely large. Since it was difficult
to mold them, a bending test was not performed.
Comparative Examples 11 and 12
[0260] To each of the same cellulose acetate butyrate and cellulose
acetate propionate before grafting as those used in Examples 23 and
24 respectively, triethyl citrate (trade name: Citroflex-2
manufactured by Pfizer Inc.) was added as a plasticizer such that
the content became 27% by mass based on the whole resin
composition. This was mixed by an extruder mixer (HAAKE MiniLab
Rheomex extruder (Model CTW5, Thermo Electron Corp., Waltham,
Mass.)) at a temperature of 180.degree. C. and a screw rotation
speed of 60 rpm to prepare a cellulose acetate butyrate resin
composition and a cellulose acetate propionate resin
composition.
[0261] The resin compositions were evaluated in the same manner as
in Example 1. The results are shown in Table 3.
[0262] Note that when each of the resin compositions was casted, a
phase separation occurred and a uniform film could not be prepared.
Thus, a tensile test was not performed.
Comparative Example 13
[0263] To compare with Example 26, a resin composition composed of
cellulose acetate and triethyl citrate as a plasticizer was
prepared in accordance with the same manner as in Comparative
Example 2 except that the addition amount of the plasticizer was
changed to 63% by mass based on the whole resin composition. The
total amount of plasticizer and acetyl group was set to be equal to
the amount of cardanol of Example 26. The resin composition was
evaluated in the same manner as in Example 1. The results are shown
in Table 4.
[0264] Note that when the resin composition was casted, a phase
separation occurred and a uniform film could not be prepared. Thus,
a tensile test was not performed.
Comparative Example 14
[0265] An unsaturated bond of cardanol represented by the above
Formula (2) (LB-7000: a mixture of 3-pentadecylphenol (about 5%),
3-pentadecylphenol monoene (about 35%), 3-pentadecylphenol diene
(about 20%), 3-pentadecylphenol triene (about 40%); manufactured by
Tohoku Chemical Industries, Ltd.) was chemically bound to a hydroxy
group of a cellulose (trade name: KC Flock W-50G manufactured by
Nippon Paper Chemicals) to obtain cardanol-grafted cellulose. More
specifically, the cardanol-grafted cellulose was prepared in
accordance with the following procedure.
[0266] In a dry box, a reaction solvent was prepared from
borontrifluoride diethyl ether (BF.sub.3-OEt.sub.2) (manufactured
by Kanto Chemical Co., Inc.) (80 mL) and methylene chloride (100
mL) (manufactured by Kanto Chemical Co., Inc.) under a nitrogen gas
atmosphere. To this, cellulose (2 g) was added and the mixture was
stirred at room temperature for 2 hours.
[0267] Thereafter, the cellulose was separated by filtration from
the reaction solvent and dried under vacuum. Thereafter, to this,
liquid-state cardanol (LB-7000) (100 mL) as mentioned above was
added and a grafting reaction was performed while stirring at room
temperature for 3 hours. After completion of the reaction, a
product was separated by filtration, washed with acetone, extracted
by Soxhlet and dried under vacuum at 105.degree. C. for 5 hours to
obtain a desired cardanol-grafted cellulose composition (2.5 g).
DS.sub.CD was obtained from a yield, and DS.sub.CD was 0.16.
[0268] Note that the composition did not melt even if heated and
did not exhibit thermoplasticity. Furthermore, since the
composition could be neither molded nor casted, evaluation, such as
a bending test and tensile test, was not performed.
Example 27
[0269] To the cellulose resin (grafted cellulose acetate) (90 parts
by mass) obtained in Example 5, TPU (adipate ester based TPU, trade
name: Rezamin P6165 manufactured by Dainichiseika Color &
Chemicals Mfg. Co., Ltd.) (10 parts by mass) was added. The mixture
was mixed by an extruder mixer (HAAKE MiniLab Rheomex extruder,
Model CTW5, Thermo Electron Corp., Waltham, Mass.) at a temperature
of 200.degree. C. and a screw rotation speed of 60 rpm to prepare a
cellulose resin composition.
[0270] The obtained cellulose resin composition was evaluated in
accordance with the following procedure. The results are shown in
Table 5. In the table, A-1 represents TPU used in this Example.
[0271] Glass transition temperature (heat resistance evaluation)
and water absorption rate were obtained by measurement in the same
manner as in Example 1.
[0272] The obtained cellulose resin composition was molded in the
following conditions.
(Molding Conditions)
[0273] Temperature: 200.degree. C., Time: 2 minutes, Pressure: 100
kgf (9.8.times.10.sup.2 N),
[0274] Size of compact (compact 1): Thickness: 2 mm, Width: 13 mm,
Length: 80 mm.
[0275] Size of compact (compact 2): Thickness: 4 mm, Width: 10 mm,
Length: 80 mm.
[Evaluation of Izod Impact Strength]
[0276] Compact 2 obtained by molding in the above was subjected to
the measurement of Izod impact strength (provided with a notch) of
compact in accordance with JIS K7110.
[Bending Test]
[0277] Compact 1 obtained by molding in the above was subjected to
a bending test in accordance with JIS K7171.
Example 28
[0278] A cellulose resin composition was produced and evaluated in
the same manner as in Example 27 except that caprolactone based TPU
(trade name: Rezamin P4038S manufactured by Dainichiseika Color
& Chemicals Mfg. Co., Ltd.) was used as TPU (represented by A-2
in the table). The results are shown in Table 5.
Example 29
[0279] A cellulose resin composition was produced and evaluated in
the same manner as Example 27 except that silicone-copolymerized
adipate based TPU (trade name: Rezamin PS62470 manufactured by
Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was used as TPU
(represented by A-3 in the table). The results are shown in Table
5.
Reference Example 1
[0280] A cellulose resin composition was produced and evaluated in
the same manner as Example 27 except that cyclohexane dicarboxylic
acid ester (product name: Hexamoll DINCH, manufactured by BASF
Ltd.) serving as a plasticizer was used in place of TPU. The
results are shown in Table 5.
Examples 30 to 35
[0281] To the cellulose resin (grafted cellulose acetate) obtained
in Example 5, a polydimethyl siloxane compound (silicone compound)
shown in Table 6 and manufactured by Shin-Etsu Chemical Co., Ltd.
was added in accordance with the blending conditions shown in Table
7. This was mixed by an extruder mixer (HAAKE MiniLab Rheomex
extruder, Model CTW5, Thermo Electron Corp., Waltham, Mass.) at a
temperature of 200.degree. C. and a screw rotation speed of 50 rpm.
In this manner, cellulose resin compositions were prepared.
[0282] The obtained cellulose resin compositions were evaluated in
accordance with the following procedure. The results are show in
Table 7.
[0283] Glass transition temperature (heat resistance evaluation)
and water absorption rate were obtained by measurement in the same
manner as in Example 1.
[0284] The obtained cellulose resin compositions were molded in the
following conditions.
(Molding Conditions)
[0285] Temperature: 200.degree. C., Time: 2 minutes, Pressure: 100
kgf (9.8.times.10.sup.2 N),
[0286] Size of compact (compact 1): Thickness: 2 mm, Width: 13 mm,
Length: 80 mm.
[0287] Size of compact (compact 2): Thickness: 4 mm, Width: 10 mm,
Length: 80 mm.
[Evaluation of Izod Impact Strength]
[0288] Compact 2 obtained by molding in the above was subjected to
the measurement of Izod impact strength (provided with a notch) of
compact in accordance with JIS K7110.
[Bending Test]
[0289] Compact 1 obtained by molding in the above was subjected to
a bending test in accordance with JIS K7171.
[Evaluation of Dispersed Particle Diameter]
[0290] The obtained resin composition was melted on a hot plate of
200.degree. C. to prepare a preparation, which was observed under
an optical microscope (trade name: VHX-500, manufactured by KEYENCE
Corporation) at a magnification of 1000.times. to obtain diameters
of dispersed particles of the polysiloxane compound.
Examples 36 to 44
[0291] Cellulose resin compositions were prepared and evaluated in
the same manner as Examples 30 to 35 except that the cellulose
resin of Example 7 was used in place of the cellulose resin of
Example 5 and a polysiloxane compound (silicone compound) was added
in accordance with the blending conditions shown in Table 8. The
results are shown in Table 8.
Reference Example 2
[0292] A cellulose resin composition was prepared and evaluated in
the same manner as Examples 30 to 35 except that B-11 was used as
the polysiloxane compound (silicone compound). The results are
shown in Table 7.
Reference Example 3
[0293] A cellulose resin composition was prepared and evaluated in
the same manner as Examples 36 to 41 except that B-10 was used as
the polysiloxane compound (silicone compound). The results are
shown in Table 8.
Reference Example 4
[0294] A cellulose resin composition was prepared and evaluated in
the same manner as Examples 36 to 41 except that B-11 was used as
the polysiloxane compound (silicone compound). The results are
shown in Table 8.
TABLE-US-00001 TABLE 1A Example Example Example Example Example
Example 1 2 3 4 5 6 Amount of DS.sub.Ace 2.1 2.1 2.1 2.1 2.1 2.1
acetyl group Mass fraction 16 20 21 21 23 26 (%) Amount of
DS.sub.CD 0.90 0.55 0 0 0 0 cardanol modified with derivative
succinic acid DS.sub.CD 0 0 0.55 0.80 0.44 0.30 modified with
monochloro acetic acid Mass fraction 56 46 43 53 38 29 (%) Amount
of DS.sub.XX 0 0 0 0 0 0 reactive Mass fraction 0 0 0 0 0 0
hydrocarbon (%) compound Addition amount of plasticizer 0 0 0 0 0 0
(% by mass) Bending strength (MPa) 38 48 50 36 60 83 Bending
elastic modulus (GPa) 0.80 1.1 1.2 0.80 1.4 1.9 Bend-breaking
strain (%) >10 >10 >10 >10 >10 >10 Tensile
strength (MPa) 29 36 38 27 45 59 Tensile elastic modulus (GPa) 0.6
0.9 1.0 0.6 1.2 1.7 Tensile breaking strain (%) 57 55 53 57 51 48
Glass transition temperature 125 134 147 139 142 150 (.degree. C.)
(heat resistance) Thermoplasticity (press .smallcircle.
.smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. moldability) Water absorption rate (%) 1.1 1.5 1.2
0.94 1.3 1.7 Plant component ratio (%) 71 70 73 76 72 71
TABLE-US-00002 TABLE 1B Example Example Example Example Example
Example 7 8 9 10 11 12 Amount of DS.sub.Ace 2.1 2.1 2.1 2.1 2.1 2.1
acetyl group Mass fraction 25 26 21 24 25 31 (%) Amount of
DS.sub.CD 0 0 0 0 0 0 cardanol modified with derivative succinic
acid DS.sub.CD 0.30 0.22 0.44 0.24 0.30 0.08 modified with
monochloro acetic acid Mass fraction 28 22 36 22 29 9.4 (%) Amount
of DS.sub.XX xx = BC xx = BC xx = BC xx = BC xx = BC xx = BC
reactive 0.14 0.27 0.22 0.42 0.07 0.16 hydrocarbon Mass fraction
4.0 8.0 5.4 12 1.8 5.7 compound (%) Addition amount of plasticizer
0 0 0 0 0 0 (% by mass) Bending strength (MPa) 113 118 106 112 94
95 Bending elastic modulus (GPa) 2.2 2.6 2.1 2.2 1.9 2.9
Bend-breaking strain (%) >10 >10 >10 >10 >10 6.5
Tensile strength (MPa) 69 72 66 70 64 75 Tensile elastic modulus
(GPa) 1.6 1.8 1.6 1.6 1.5 1.9 Tensile breaking strain (%) 48 47 52
47 50 30 Glass transition temperature 154 155 144 156 152 158
(.degree. C.) (heat resistance) Thermoplasticity (press
.smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. moldability) Water absorption rate (%)
1.3 1.6 1.1 1.2 1.4 1.9 Plant component ratio (%) 68 64 68 61 69 62
Example Example Example Example 13 14 15 16 Amount of DS.sub.Ace
2.1 2.1 2.1 2.1 acetyl group Mass fraction 24 20 18 20 (%) Amount
of DS.sub.CD 0 0 0 0 cardanol modified with derivative succinic
acid DS.sub.CD 0.27 0.40 0.55 0.30 modified with monochloro acetic
acid Mass fraction 25 30 39 23 (%) Amount of DS.sub.XX xx = BAA xx
= BAA xx = BAA xx = BAA reactive 0.15 0.40 0.28 0.52 hydrocarbon
Mass fraction 7.3 16 11 21 compound (%) Addition amount of
plasticizer 0 0 0 0 (% by mass) Bending strength (MPa) 106 107 93
95 Bending elastic modulus (GPa) 2.5 2.0 1.9 2.1 Bend-breaking
strain (%) >10 >10 >10 >10 Tensile strength (MPa) 65 65
63 64 Tensile elastic modulus (GPa) 1.8 1.5 1.4 1.6 Tensile
breaking strain (%) 45 46 48 45 Glass transition temperature 148
150 142 147 (.degree. C.) (heat resistance) Thermoplasticity (press
.smallcircle. .smallcircle. .smallcircle. .smallcircle.
moldability) Water absorption rate (%) 1.0 0.72 0.68 0.65 Plant
component ratio (%) 65 60 66 55
TABLE-US-00003 TABLE 1C Compara- Compara- Compara- Compara-
Compara- Example Example Example Example tive tive tive tive tive
17 18 19 20 Example 1 Example 2 Example 3 Example 4 Example 5
Amount of DS.sub.Ace 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 acetyl
group Mass fraction 26 27 26 22 36 20 16 24 29 (%) Amount of
DS.sub.CD 0 0 0 0 0 0 0 0 0 cardanol modified with derivative
succinic acid DS.sub.CD 0.17 0.13 0.20 0.30 0 0 0 0 0 modified with
monochloro acetic acid Mass fraction 17 13 20 25 0 0 0 0 0 (%)
Amount of DS.sub.XX xx = PPA xx = PPA xx = CHC xx = BCC 0 0 0 0 xx
= PPA reactive 0.25 0.35 0.22 0.30 0.47 hydrocarbon Mass fraction
9.7 14 7.1 13 0 0 0 0 20 compound (%) Addition amount of
plasticizer 0 0 0 0 0 45 56 34 0 (% by mass) Bending strength (MPa)
106 108 111 109 -- 15 11 24 -- Bending elastic modulus (GPa) 2.5
2.6 2.5 2.5 -- 0.41 0.29 0.72 -- Bend-breaking strain (%) >10
>10 >10 >10 -- >10 >10 >10 -- Tensile strength
(MPa) 65 66 68 67 60 -- -- -- 52 Tensile elastic modulus (GPa) 1.4
1.4 1.6 1.5 2.3 -- -- -- 1.9 Tensile breaking strain (%) 60 58 55
50 9.0 -- -- -- 16 Glass transition temperature 143 142 146 150 227
40 25 71 152 (.degree. C.) (heat resistance) Thermoplasticity
(press .smallcircle. .smallcircle. .smallcircle. .smallcircle. x
.smallcircle. .smallcircle. .smallcircle. x moldability) Water
absorption rate (%) 1.9 1.8 1.8 1.4 17 5.1 4.3 5.7 4.5 Plant
component ratio (%) 61 58 64 65 64 35 28 42 51
TABLE-US-00004 TABLE 2 Example Example Comparative Comparative
Comparative 21 22 Example 6 Example 7 Example 8 Amount of
DS.sub.Ace 2.4 2.4 2.4 2.4 2.4 acetyl group Mass fraction 31 24 31
39 24 (%) Amount of DS.sub.CD 0.19 0.50 0 0 0 cardanol modified
with derivative monochloro acetic acid Mass fraction 20 40 0 0 0
(%) Addition amount of plasticizer 0 0 0 20 40 (% by mass) Bending
strength (MPa) 120 59 -- 50 20 Bending elastic modulus (GPa) 2.8
1.5 -- 2.3 0.80 Bend-breaking strain (%) >10 >10 -- >10
>10 Tensile strength (MPa) 55 38 58 -- -- Tensile elastic
modulus (GPa) 1.8 1.0 2.1 -- -- Tensile breaking strain (%) 34 53
11 -- -- Glass transition temperature 154 134 216 90 63 (.degree.
C.) (heat resistance) Thermoplasticity (press .smallcircle.
.smallcircle. x .smallcircle. .smallcircle. moldability) Water
absorption rate (%) 2.1 1.2 9.0 3.1 2.6 Plant component ratio (%)
66 71 61 49 36
TABLE-US-00005 TABLE 3 Example Example Example Comparative
Comparative Comparative Comparative 23 24 25 Example 9 Example 10
Example 11 Example 12 Amount of DS.sub.Ace 1.0 0.18 0.18 1.0 0.18
1.0 0.18 acetyl group Mass fraction 9.8 1.8 2.0 13 2.5 9.8 1.8 (%)
Amount of DS.sub.Bu or DS.sub.Pr DS.sub.Bu DS.sub.Pr DS.sub.Pr
DS.sub.Bu DS.sub.Pr DS.sub.Bu DS.sub.Pr butyryl/ 1.66 2.49 2.49
1.66 2.49 1.66 2.49 propionyl Mass fraction 27 27 36 37 46 27 34
group (%) Amount of DS.sub.CD 0.34 0.33 0.21 0 0 0 0 cardanol
modified with derivative monochloro acetic acid Mass fraction 27 27
19 0 0 0 0 (%) Amount of DS.sub.XX 0 0 xx = BC 0 0 0 0 reactive
0.10 hydrocarbon Mass fraction 0 0 2.7 0 0 0 0 compound (%)
Addition amount of plasticizer 0 0 0 0 0 27 27 (% by mass) Bending
strength (MPa) 45 49 60 -- -- 23 15 Bending elastic modulus (GPa)
1.3 1.4 1.6 -- -- 0.79 0.82 Bend-breaking strain (%) >10 >10
>10 -- -- >10 >10 Tensile strength (MPa) 35 39 43 36 40 --
-- Tensile elastic modulus (GPa) 0.85 0.87 1.0 1.0 1.1 -- --
Tensile breaking strain (%) 100 98 82 55 52 -- -- Glass transition
temperature 94 92 100 135 143 59 59 (.degree. C.) (heat resistance)
Thermoplasticity (press .smallcircle. .smallcircle. .smallcircle.
.DELTA. .DELTA. .smallcircle. .smallcircle. moldability) Water
absorption rate (%) 0.65 0.76 0.74 2.6 3.1 1.5 1.6 Plant component
ratio (%) 60 61 57 50 52 36 38
TABLE-US-00006 TABLE 4 Example Comparative 26 Example 13 Amount of
Mass fraction 24 24 cellulose (%) Amount of DS.sub.Ace 0 2.1 acetyl
group Mass fraction 0 13 (%) Amount of DS.sub.CD 1.49 0 cardanol
modified with derivative monochloro acetic acid Mass fraction 76 0
(%) Addition amount of plasticizer 0 63 (% by mass) Bending
strength (MPa) 25 9 Bending elastic modulus (GPa) 0.38 0.20
Bend-breaking strain (%) >10 >10 Tensile strength (MPa) 17 --
Tensile elastic modulus (GPa) 0.26 -- Tensile breaking strain (%)
22 -- Glass transition temperature 84 21 (.degree. C.) (heat
resistance) Thermoplasticity (press .largecircle. .largecircle.
moldability) Water absorption rate (%) 1.9 4.0 Plant component
ratio (%) 89 24
TABLE-US-00007 TABLE 5 Example Example Example Example Reference 27
28 29 5 Example 1 Amount of cellulose resin 90 90 90 100 90 (% by
mass) TPU A-1 10 A-2 10 A-3 10 -- -- (% by mass) Plasticizer (% by
mass) -- -- -- -- 10 Impact strength (kJ/m.sup.2) 8.5 8.4 12.6 6.7
7.3 Bending strength (MPa) 57 58 55 60 50 Bending elastic modulus
(GPa) 1.3 1.3 1.3 1.4 1.1 Bend-breaking strain (%) >10 >10
>10 >10 >10 Glass transition temperature 141 140 140 142
135 (.degree. C.) (heat resistance) Water absorption rate (%) 1.3
1.3 1.2 1.3 1.3
TABLE-US-00008 TABLE 6 Substit- Substit- Average uent 1 uent 2
Viscos- molec- Product Average Average ity ular No. name content
(%) content (%) (mm.sup.2/s) weight B-1 KF8002 Side-chain -- 1100
24000 amino group 0.94 B-2 KF8005 Side-chain -- 1200 25000 amino
group 0.15 B-3 X22-173DX Epoxy group -- 65 4500 at an end 0.96 B-4
KF101 Side-chain -- 1500 27000 epoxy group 12.3 B-5 KF1001
Side-chain -- 17000 67000 epoxy group 1.23 B-6 X22-4039 Side-chain
-- 90 6000 carbinol group 1.76 B-7 KF50-3000cs Side-chain -- 3000
36000 phenyl group 9.6 B-8 X22-2000 Side-chain Side-chain 190 8000
phenyl group epoxy group 9.6 6.94 B-9 X22-3000T Side-chain
Side-chain 2500 32000 aralkyl group epoxy group 7.5 17.2 B-10
X22-715 Fatty acid -- 14000 -- ester group 73 B-11 KF96-1000cs --
-- 1000 23000
TABLE-US-00009 TABLE 7 Example Example Example Example Example
Example Example Reference 30 31 32 33 34 35 5 Example 2 Amount of
cellulose resin 97 97 97 97 97 97 100 97 (% by mass) Silicone
compound B-1 B-2 B-3 B-5 B-7 B-8 -- B-11 (% by mass) 3 3 3 3 3 3 3
Diameter of dispersed particle 0.5-1 3-6 8-12 6-10 5-8 0.5-1 --
10-20 (.mu.m) Impact strength (kJ/m.sup.2) 8.4 8.2 10.9 9.9 10.1
7.5 6.7 5.6 Bending strength (MPa) 61 62 63 62 60 60 60 60 Bending
elastic modulus (GPa) 1.4 1.4 1.3 1.5 1.5 1.4 1.4 1.5 Bend-breaking
strain (%) >10 >10 >10 >10 >10 >10 >10 >10
Glass transition temperature 143 144 145 141 143 142 142 134
(.degree. C.) (heat resistance) Water absorption rate (%) 1.2 1.2
1.2 1.2 1.3 1.3 1.3 1.3
TABLE-US-00010 TABLE 8 Example Example Example Example Example
Example Example 36 37 38 39 40 41 42 Amount of cellulose resin 97
97 97 97 97 97 97 (% by mass) Silicone compound 1 B-2 B-4 B-5 B-6
B-7 B-9 B-5 (% by mass) 3 3 3 3 3 3 2.1 Silicone compound 2 -- --
-- -- -- -- B-9 (% by mass) 0.9 Diameter of dispersed particle 5-8
0.5-1 6-10 5-8 5-8 0.1-1 3-6 (.mu.m) Impact strength (kJ/m.sup.2)
6.2 6.5 5.3 6.6 7.0 5.7 7.5 Bending strength (MPa) 114 115 114 113
113 115 114 Bending elastic modulus (GPa) 2.4 2.5 2.4 2.3 2.2 2.3
2.3 Bend-breaking strain (%) >10 >10 >10 >10 >10
>10 >10 Glass transition temperature 155 154 157 150 153 154
154 (.degree. C.) (heat resistance) Water absorption rate (%) 1.3
1.3 1.3 1.4 1.4 1.3 1.4 Example Example Example Reference Reference
43 44 7 Example 3 Example 4 Amount of cellulose resin 97 97 100 97
97 (% by mass) Silicone compound 1 B-5 B-3 -- B-10 B-11 (% by mass)
1.5 2.1 3 3 Silicone compound 2 B-9 B-10 -- -- -- (% by mass) 0.5
0.9 Diameter of dispersed particle 3-6 3-6 -- <0.1 10-20 (.mu.m)
Impact strength (kJ/m.sup.2) 7.4 7.3 4.4 4.2 4.0 Bending strength
(MPa) 113 113 113 112 113 Bending elastic modulus (GPa) 2.2 2.4 2.2
2.2 2.3 Bend-breaking strain (%) >10 >10 >10 >10 >10
Glass transition temperature 153 153 154 150 152 (.degree. C.)
(heat resistance) Water absorption rate (%) 1.4 1.3 1.3 1.3 1.4
[0295] When Examples 1 to 6 are compared to Comparative Example 1,
the cardanol-grafted cellulose resins (an acetyl group is also
added to a cellulose hydroxy group) of the examples each had
thermoplasticity (press moldability) and excellent bending
properties without reducing a plant component ratio, and further
tensile properties (particularly, breaking strain) and water
resistance (water absorption rate) were improved, compared to the
cellulose derivative (cellulose acetate) before grafting which had
no thermoplasticity. Furthermore, when Examples 1 to 6 are compared
to Comparative Examples 2 to 4, the cardanol-grafted cellulose
resins (an acetyl group is also added to a cellulose hydroxy group)
of the examples were more improved in bending properties, tensile
properties and water resistance than the cellulose derivatives
before grafting (cellulose acetate) which contained the
plasticizer. In addition, high heat resistance (glass transition
temperature) was obtained without reducing the plant component
ratio.
[0296] As shown in Examples 7 to 20, bending properties
(particularly, bending strength) and tensile properties
(particularly, tensile strength) can be even more improved while
obtaining high water resistance by grafting with not only cardanol
but also a reactive hydrocarbon.
[0297] In Examples 21 and 22 and Comparative Examples 6 to 8,
compared to Examples 1 to 20 and Comparative Examples 1 to 5, the
amount of acetyl group added to a cellulose hydroxy group is
increased. Even in these case, when Examples 21 and 22 are compared
to Comparative Example 6, the cardanol-grafted cellulose resins of
the examples each had thermoplasticity and excellent bending
properties without reducing a plant component ratio, and further
tensile properties (particularly, breaking strain) and water
resistance were improved, compared to the cellulose derivative
before grafting which had no thermoplasticity. Furthermore, when
Examples 21 and 22 are compared to Comparative Examples 7 and 8,
the cardanol-grafted cellulose resins of the examples were more
improved in bending properties (particularly, bending strength),
tensile properties and water resistance than the cellulose
derivatives before grafting which contained the plasticizer. In
addition, high heat resistance was obtained without reducing the
plant component ratio.
[0298] As shown in Comparative Examples 2 to 4, 7 and 8 containing
plasticizer, excellent heat resistance was not obtained by adding
the plasticizer alone. According to the exemplary embodiment, not
only thermoplasticity can be imparted to a cellulose resin but also
excellent heat resistance can be obtained.
[0299] Furthermore, as shown in Comparative Example 5 in which a
reactive hydrocarbon alone was grafted, thermoplasticity was not
obtained only by grafting a reactive hydrocarbon alone, and bending
properties, tensile properties (particularly, breaking strain) and
water resistance were not improved. According to the exemplary
embodiment, not only thermoplasticity can be imparted to a
cellulose resin but also excellent bending properties, tensile
properties (particularly, breaking strain) and water resistance can
be obtained.
[0300] Examples 23 to 25 and Comparative Examples 9 to 12, each are
an example of a cellulose resin prepared by using a cellulose
derivative having not only an acetyl group but also a butyryl group
or a propionyl group added to a hydroxy group. Even in these case,
when Examples 23 to 25 are compared to Comparative Examples 9 and
10, in the cardanol-grafted cellulose resins of the examples,
excellent thermoplasticity and bending properties were obtained
without reducing the plant component ratio, and further tensile
properties (particularly breaking strain) and water resistance were
improved, compared to the cellulose derivatives before grafting.
Furthermore, when Examples 23 to 25 and Comparative Examples 11 and
12 are compared, the cardanol-grafted cellulose resins of the
examples were more improved in bending properties (particularly,
bending strength), tensile properties and water resistance than the
cellulose derivatives before grafting which contained the
plasticizer. In addition, high heat resistance was obtained without
reducing the plant component ratio.
[0301] Example 26 is an example of a cellulose resin prepared by
using cellulose having a cellulose hydroxy group to which an acyl
group such as an acetyl group is not added. Even in this case, when
Example 26 is compared to Comparative Example 13, the
cardanol-grafted cellulose resin of the example was more improved
in bending properties (particularly, bending strength), tensile
properties and water resistance than the cellulose derivative of
Comparative Example 13, in which the cellulose derivative
(cellulose acetate) contained a plasticizer (the weight ratio of
the cellulose component is the same as the example 26). In
addition, high heat resistance was obtained without reducing the
plant component ratio.
[0302] As described above, according to the examples, it is
possible to provide a cellulose resin improved in water resistance
and having good thermoplasticity (press moldability) and sufficient
heat resistance while maintaining a high plant component ratio
(high vegetism). Furthermore, a press compact having high bending
properties can be obtained and a film compact can be improved in
tensile properties (particularly, toughness). Furthermore,
according to the examples, a grafted cellulose resin having a high
plant component ratio as well as high utilization ratio of
non-edible parts can be obtained.
[0303] In Table 5, when Examples 27 to 29 containing a
thermoplastic polyurethane elastomer (TPU) are compared to Example
5 containing no TPU, it was found that the obtained cellulose resin
compositions in which TPU was added to a cellulose resin were
excellent in shock resistance while maintaining satisfactory
strength, heat resistance (Tg) and water resistance. In particular,
as shown in Example 29, it was found that a resin composition
having even more excellent shock resistance than any other resin
compositions to which general TPU was added, can be obtained by
adding TPU copolymerized with silicon.
[0304] Furthermore, the resin compositions of Examples 27 to 29, in
which TPU was added thereto, exhibited the equal or larger
meltability in the same molding conditions, and exhibited good
thermoplasticity, compared to the cardanol-added cellulose resin of
Example 5, which contained no TPU. Note that, in the cardanol-added
cellulose resin of Reference Example 1, in which a plasticizer was
added thereto, the effect of improving shock resistance was not
obtained, and strength and heat resistance decreased.
[0305] When Examples 30 to 35 are compared to Example 5 in Table 7,
and Examples 36 to 44 are compared to Example 7 in Table 8, it was
found that a resin composition in which a modified polydimethyl
siloxane compound was added to a cellulose resin was excellent in
shock resistance while maintaining satisfactory strength, heat
resistance (Tg) and water resistance. In particular, as shown in
Examples 42 to 44, it was found that a resin composition having
even more excellent shock resistance can be obtained by adding two
types of modified polydimethyl siloxane compounds in
combination.
[0306] Furthermore, the resin compositions of Examples 30 to 44, in
which a modified polydimethyl siloxane compound was added thereto,
exhibited equal or larger meltability, compared to the
cardanol-added cellulose resins of Examples 5 and 7 in the same
molding conditions, and exhibited good thermoplasticity.
[0307] On the other hand, in Reference Example 2 and Reference
Example 4, in which polydimethyl siloxane (B-11) having no organic
substituent was added thereto, an effect of improving shock
resistance was not obtained. Furthermore, also in Reference Example
3, in which a modified polydimethyl siloxane (B-10) having an
average content of the organic substituent exceeding 70% by mass
was singly added, an effect of improving shock resistance was not
obtained.
[0308] Having thus described the present invention with reference
to the exemplary embodiments, the present invention is not limited
to the above-described exemplary embodiments. Various modifications
understandable to those skilled in the art may be made to the
constitution and details of the present invention within the scope
thereof.
[0309] This application claims the right of priority based on
Japanese Patent Application No. 2009-231670 filed Oct. 5, 2009, No.
2010-105509 filed Apr. 30, 2010 and No. 2010-156238 filed Jul. 8,
2010, the entire content of which are incorporated herein by
reference.
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